Flame retardant compositions

ABSTRACT

Organic polymeric substrates, for example polyolefins such as polypropylene, can be made flame retardant by the incorporation of a synergistic mixture of (i) at least one sterically hindered amine stabilizer, (ii) at least one conventional flame retardant selected from the group consisting of the organohalogen, phosphorus containing, isocyanurate and melamine based flame retardants and (iii) at least one acid scavenger. The compositions of the invention combine good flame retardant properties with light stability and good mechanical properties. Polyolefin molded articles are stabilized against light, heat and oxygen and made flame retardant with the incorporation of at least one sterically hindered amine and at least one conventional flame retardant, while allowing normally high levels of flame-retardant fillers to be greatly reduced or eliminated.

This application claims the benefit under 35 USC 119(e) of U.S.provisional app. No. 60/419,260, filed Oct. 17, 2002.

The instant invention pertains to a novel method of flame retarding apolymeric substrate by adding thereto an effective flame retardingamount of a synergistic mixture of at least one sterically hinderedamine stabilizer, at least one conventional flame retardant and at leastone acid scavenger.

The instant invention also pertains to polyolefin molded articles thatare stabilized against light, heat and oxygen and made flame retardantwith the incorporation therein of at least one sterically hindered aminestabilizer and at least one conventional flame retardant, while allowingnormally high levels of flame-retardant fillers to be greatly reduced oreliminated.

BACKGROUND OF THE INVENTION

U.S. Pat. No. 5,096,950 discloses the co-use of certain NOR(N-alkoxy)hindered amines with a brominated Sb₂O₃-containing flame retardant inpolypropylene.

U.S. Pat. No. 5,393,812 discloses polyolefin compositions which are madeflame retardant by a combination of a halogenated hydrocarbyl phosphateor phosphonate ester flame retardant in combination with a alkoxyaminefunctional hindered amine.

U.S. Pat. No. 5,844,026 discloses polyolefin compositions comprisingcertain NOR hindered amines and certain traditional flame retardants.

U.S. Pat. No. 6,117,995 discloses that certain N-alkoxy hindered aminesmay be used as flame retardants for organic polymers.

U.S. Pat. No. 6,271,377 discloses polyolefin compositions that compriseN-hydroxyalkoxy hindered amines and a halogenated flame retardant.

U.S. Pat. No. 6,309,987 and equivalent WO 99/54530 teach polyolefinnon-woven flame retardant fabrics that comprise N-alkoxyamines.

U.S. Pat. No. 6,262,161 discloses random interpolymers, for examplepolymers of ethylene and/or one or more α-olefin monomers with one ormore vinyl aromatic monomers, with improved ignition resistance thatcomprises a filler and at least one other component which may be ahindered amine stabilizer.

A Revolutionary UV Stable Flame Retardant System for Polyolefins—R.Srinivasan, A. Gupta and D. Horsey, Int. Conf. Addit. Polyolefins 1998,69–83, teaches polyolefins comprising certain NOR hindered amines withhalogen and phosphorus containing traditional flame retardants.

Advances in a Revolutionary Flame Retardant System for Polyolefins—R.Srinivasan, B. Rotzinger, Polyolefins 2000, Int. Conf. Polyolefins 2000,571–581, teaches polyolefins comprising certain NOR hindered amines withbrominated and phosphorus containing flame retardants.

N. Kaprinidis and R. King, in an abstract posted on the Society ofPlastics Engineers website, posted September 2001, discuss the use ofNOR hindered amines as flame retardants in polyolefins. The abstract isfor a paper submitted to the Polymer Modifiers and Additives Divisionsubsection to be presented at the Polyolefins 2002 conference inHouston, Tex., Feb. 24, 2002. The website is www.PMAD.org.

EP 0792911 A2, discloses polyolefin compositions that comprisealkoxyamine functional hindered amines andtris(trihalogenopentyl)phosphate flame retardants.

WO 99/00450, copending U.S. application Ser. No. 09/502,239, filed Nov.3, 1999, and Ser. No. 09/714,717, filed Nov. 16, 2000, disclose the useof certain N-alkoxy hindered amines as flame retardants.

EP 1038912 discloses specific hydrocarbyloxy hindered amine compounds asflame retardants.

Research Disclosure, September. 2000, No. 437087, June 2000, No. 434095and December 2000, No. 440128 also disclose the efficacy of certainhydrocarbyloxy hindered amine compounds as flame retardants.

U.S. Pat. No. 6,225,387 discloses organohalide flame retardant polymercompositions.

The flame retardant (FR) market today is comprised of products whichfunction to interfere with the combustion process by chemical and/orphysical means. Mechanistically these FRs have been proposed to functionduring combustion of an article in either the gas phase, the condensedphase or both. The organohalogens are proposed to generate halogenspecies (e.g. HX) which interferes in the gas phase with free radicalorganic “fuel” from the polymer substrate. Synergists are proposed toreact with HX to form additional chemical species which interfere withcombustion in the gas phase, such as reaction of antimony oxide with HXto form antimony halide and water vapor. Antimony compounds such asantimony trioxide also act as a radical scavenger forming antimonyhalides. Thus, it can inhibit the propagation of the fire.

Although antimony compounds are efficient in terms of cost performance,it recently raised a lot of concern because of the toxicity of thebyproducts which are formed during combustion in the presence of ahalogenated flame retardant. Antimony oxides often contain trace amountsof arsenic compounds which are suspected carcinogens. Because of theseecological concerns, there is a motion to replace antimony trioxide inthe present commercial flame retardant applications. However, it is verydifficult to find an effective synergist which is both enviromentallyfriendly and efficient as far as the cost performance is concerned.

Another reason to add flame retardant additives is to prevent drippingduring the application of the fire. Dripping during combustion is theprocess of the separation of parts of the polymer from the matrix in theshape of droplets. Most often, the droplets are flaming and are imposingtremendous danger for fire spread. It is a common measure to add fillerssuch as talc in large amounts to the polymer, with some negativeconsequences on the mechanical properties. Fillers sometimes usedinclude calcium carbonate, magnesium carbonate, zinc borate, silicates,silicones, glass fibres, glass bulbs, asbestos, kaolin, mica, bariumsulfate, calcium sulfate, metal oxides, hydrates and hydroxides such aszinc oxide, magnesium hydroxide, alumina trihydrate, silica, calciumsilicate and magnesium silicate.

It has been found that polymers with good flame retardant properties areprepared when a sterically hindered amine stabilizer is added theretotogether with a conventional organohalogen flame retardant, phosphoruscontaining flame retardant, isocyanurate flame retardant or melaminebased flame retardant and with an acid scavenger. With this combination,flame-retardant fillers or conventional fillers may be largely reducedor replaced. As the instant hindered amine compounds are active asstabilizers, the polymer compositions of the invention are efficientlyprotected from the deleterious effects of light, oxygen and/or heat.

DETAILED DISCLOSURE

The instant invention pertains to a flame retardant polymer compositionwhich comprises

(a) an organic polymer substrate and

(b) an effective flame retarding amount of a synergistic mixture of

-   -   (i) at least one sterically hindered amine stabilizer,    -   (ii) at least one conventional flame retardant selected from the        group consisting of the organohalogen, phosphorus containing,        isocyanurate and melamine based flame retardants and    -   (iii) at least one acid scavenger.

Flame-retardant fillers are not required in order to improve the flameretardant properties and achieve a higher rating, e.g. in the UL-94burning test (infra). Consequently, the compositions of the presentinvention may contain only minor amounts of flame-retardant fillers,e.g. less than about 3%, for instance less than about 1%, for exampleless than about 0.1% by weight of the polymer component A; for example,the present compositions are essentially free of flame-retardantfillers.

Flame-retardant fillers are known in the art and are selected from thegroup consisting of magnesium hydroxide, alumina trihydrate and zincborate. Flame-retardant fillers are inorganic compounds employed forflame-retardant properties, and at high enough levels to be considered“filler”.

If conventional fillers such as talc, calcium carbonate and the like arenormally employed for instance for flow properties in order to reducethe spread of flaming droplets (not flame-retardant per se), suchconventional fillers may also be reduced with the use of the presentcompositions. For instance, the present compositions may contain onlyminor amounts of conventional fillers, for example less than about 3%,for instance less than 1%, for example less than about 0.1% by weight ofthe polymer component A; for example, the present compositions areessentially free of conventional fillers.

Further, the present invention allows for conventional fillers to takethe place of more expensive flame-retardant fillers.

The present compositions meet flame retardant specifications whilecontaining only minor amounts of antimony compounds such as Sb₂O₃, e.g.less than about 1%, for instance less than about 0.1% by weight ofcomponent (a); for example, the present compositions are essentiallyfree of antimony.

P Lymer Substrate (a)

The polymeric substrate of component (a) is any of a wide variety ofpolymeric types including polyolefins, polystyrenics, and PVC. Forexample, the polymer substrate may be selected from the group of resinsconsisting of the polyolefins, the thermoplastic olefins, styrenicpolymers and copolymers, ABS and polymers which contain hetero atoms,double bonds or aromatic rings. Specific embodiments are where component(a) is polypropylene, polyethylene, thermoplastic olefin (TPO), ABS orhigh impact polystyrene.

For example, the polymer substrate is selected from the group of resinsconsisting of the polyolefins, the thermoplastic olefins, styrenicpolymers and copolymers, and ABS.

Another embodiment of the present invention is where the polymersubstrate is selected from the group consisting of polypropylene,polyethylene, thermoplastic olefin (TPO), ABS and high impactpolystyrene.

For instance, the polymer substrate is polypropylene, polyethylene orthermoplastic olefin (TPO). Organic polymers of component A are forexample thermoplastic polymers such as polyolefins like polyethylene,polypropylene or copolymers thereof. The thermoplastic polymer is forexample polypropylene.

Further examples for organic polymers (component A) are:

1. Polymers of monoolefins and diolefins, for example polypropylene,polyisobutylene, polybut-1-ene, poly-4-methylpent-1-ene,polyvinylcyclohexane, polyisoprene or polybutadiene, as well as polymersof cycloolefins, for instance of cyclopentene or norbornene,polyethylene (which optionally can be crosslinked), for example highdensity polyethylene (HDPE), high density and high molecular weightpolyethylene (HDPE-HMW), high density and ultrahigh molecular weightpolyethylene (HDPE-UHMW), medium density polyethylene (MDPE), lowdensity polyethylene (LDPE), linear low density polyethylene (LLDPE),(VLDPE) and (ULDPE).Polyolefins, i.e. the polymers of monoolefins exemplified in thepreceding paragraph, for example polyethylene and polypropylene, can beprepared by different, and especially by the following, methods:

-   a) radical polymerisation (normally under high pressure and at    elevated temperature).-   b) catalytic polymerisation using a catalyst that normally contains    one or more than one metal of groups IVb, Vb, VIb or VIII of the    Periodic Table. These metals usually have one or more than one    ligand, typically oxides, halides, alcoholates, esters, ethers,    amines, alkyls, alkenyls and/or aryls that may be either π- or    σ-coordinated. These metal complexes may be in the free form or    fixed on substrates, typically on activated magnesium chloride,    titanium(III) chloride, alumina or silicon oxide. These catalysts    may be soluble or insoluble in the polymerisation medium. The    catalysts can be used by themselves in the polymerisation or further    activators may be used, typically metal alkyls, metal hydrides,    metal alkyl halides, metal alkyl oxides or metal alkyloxanes, said    metals being elements of groups Ia, IIa and/or IIIa of the Periodic    Table. The activators may be modified conveniently with further    ester, ether, amine or silyl ether groups. These catalyst systems    are usually termed Phillips, Standard Oil Indiana, Ziegler (Natta),    TNZ (DuPont), metallocene or single site catalysts (SSC).    2. Mixtures of the polymers mentioned under 1), for example mixtures    of polypropylene with polyisobutylene, polypropylene with    polyethylene (for example PP/HDPE, PP/LDPE) and mixtures of    different types of polyethylene (for example LDPE/HDPE).    3. Copolymers of monoolefins and diolefins with each other or with    other vinyl monomers, for example ethylene/propylene copolymers,    linear low density polyethylene (LLDPE) and mixtures thereof with    low density polyethylene (LDPE), propylene/but-1-ene copolymers,    propylene/isobutylene copolymers, ethylene/but-1-ene copolymers,    ethylene/hexene copolymers, ethylene/methylpentene copolymers,    ethylene/heptene copolymers, ethylene/octene copolymers,    ethylene/vinylcyclohexane copolymers, ethylene/cycloolefin    copolymers (e.g. ethylene/norbornene like COC), ethylene/1-olefins    copolymers, where the 1-olefin is generated in-situ;    propylene/butadiene copolymers, isobutylene/isoprene copolymers,    ethylene/vinylcyclohexene copolymers, ethylene/alkyl acrylate    copolymers, ethylene/alkyl methacrylate copolymers, ethylene/vinyl    acetate copolymers or ethylene/acrylic acid copolymers and their    salts (ionomers) as well as terpolymers of ethylene with propylene    and a diene such as hexadiene, dicyclopentadiene or    ethylidene-norbornene; and mixtures of such copolymers with one    another and with polymers mentioned in 1) above, for example    polypropylene/ethylenepropylene copolymers, LDPE/ethylene-vinyl    acetate copolymers (EVA), LDPE/ethylene-acrylic acid copolymers    (EAA), LLDPE/EVA, LLDPE/EAA and alternating or random    polyalkylene/carbon monoxide copolymers and mixtures thereof with    other polymers, for example polyamides.    4. Hydrocarbon resins (for example C₅–C₉) including hydrogenated    modifications thereof (e.g. tackifiers) and mixtures of    polyalkylenes and starch.    Homopolymers and copolymers from 1.)–4.) may have any    stereostructure including syndiotactic, isotactic, hemi-isotactic or    atactic; for example atactic polymers. Stereoblock polymers are also    included.    5. Polystyrene, poly(p-methylstyrene), poly(α-methylstyrene).    6. Aromatic homopolymers and copolymers derived from vinyl aromatic    monomers including styrene, α-methylstyrene, all isomers of vinyl    toluene, especially p-vinyltoluene, all isomers of ethyl styrene,    propyl styrene, vinyl biphenyl, vinyl naphthalene, and vinyl    anthracene, and mixtures thereof. Homopolymers and copolymers may    have any stereostructure including syndiotactic, isotactic,    hemi-isotactic or atactic; for example atactic polymers. Stereoblock    polymers are also included.    6a. Copolymers including aforementioned vinyl aromatic monomers and    comonomers selected from ethylene, propylene, dienes, nitriles,    acids, maleic anhydrides, maleimides, vinyl acetate and vinyl    chloride or acrylic derivatives and mixtures thereof, for example    styrene/butadiene, styrene/acrylonitrile, styrene/ethylene    (interpolymers), styrene/alkyl methacrylate, styrene/butadiene/alkyl    acrylate, styrene/butadiene/alkyl methacrylate, styrene/maleic    anhydride, styrene/acrylonitrile/methyl acrylate; mixtures of high    impact strength of styrene copolymers and another polymer, for    example a polyacrylate, a diene polymer or an    ethylene/propylene/diene terpolymer; and block copolymers of styrene    such as styrene/butadiene/styrene, styrene/isoprene/styrene,    styrene/ethylene/butylene/styrene or    styrene/ethylene/propylene/styrene.    6b. Hydrogenated aromatic polymers derived from hydrogenation of    polymers mentioned under 6.), especially including    polycyclohexylethylene (PCHE) prepared by hydrogenating atactic    polystyrene, often referred to as polyvinylcyclohexane (PVCH).    6c. Hydrogenated aromatic polymers derived from hydrogenation of    polymers mentioned under 6a.).    Homopolymers and copolymers may have any stereostructure including    syndiotactic, isotactic, hemi-isotactic or atactic; for example    atactic polymers. Stereoblock polymers are also included.    7. Graft copolymers of vinyl aromatic monomers such as styrene or    α-methylstyrene, for example styrene on polybutadiene, styrene on    polybutadiene-styrene or polybutadiene-acrylonitrile copolymers;    styrene and acrylonitrile (or methacrylonitrile) on polybutadiene;    styrene, acrylonitrile and methyl methacrylate on polybutadiene;    styrene and maleic anhydride on polybutadiene; styrene,    acrylonitrile and maleic anhydride or maleimide on polybutadiene;    styrene and maleimide on polybutadiene; styrene and alkyl acrylates    or methacrylates on polybutadiene; styrene and acrylonitrile on    ethylene/propylene/diene terpolymers; styrene and acrylonitrile on    polyalkyl acrylates or polyalkyl methacrylates, styrene and    acrylonitrile on acrylate/butadiene copolymers, as well as mixtures    thereof with the copolymers listed under 6), for example the    copolymer mixtures known as ABS, MBS, ASA or AES polymers.    8. Halogen-containing polymers such as polychloroprene, chlorinated    rubbers, chlorinated and brominated copolymer of    isobutylene-isoprene (halobutyl rubber), chlorinated or    sulfochlorinated polyethylene, copolymers of ethylene and    chlorinated ethylene, epichlorohydrin homo- and copolymers,    especially polymers of halogen-containing vinyl compounds, for    example polyvinyl chloride, polyvinylidene chloride, polyvinyl    fluoride, polyvinylidene fluoride, as well as copolymers thereof    such as vinyl chloride/vinylidene chloride, vinyl chloride/vinyl    acetate or vinylidene chloride/vinyl acetate copolymers.    9. Polymers derived from α,β-unsaturated acids and derivatives    thereof such as polyacrylates and polymethacrylates; polymethyl    methacrylates, polyacrylamides and polyacrylonitriles,    impact-modified with butyl acrylate.    10. Copolymers of the monomers mentioned under 9) with each other or    with other unsaturated monomers, for example acrylonitrile/butadiene    copolymers, acrylonitrilelalkyl acrylate copolymers,    acrylonitrile/alkoxyalkyl acrylate or acrylonitrile/vinyl halide    copolymers or acrylonitrile/alkyl methacrylate/butadiene    terpolymers.    11. Polymers derived from unsaturated alcohols and amines or the    acyl derivatives or acetals thereof, for example polyvinyl alcohol,    polyvinyl acetate, polyvinyl stearate, polyvinyl benzoate, polyvinyl    maleate, polyvinyl butyral, polyallyl phthalate or polyallyl    melamine; as well as their copolymers with olefins mentioned in 1)    above.    12. Homopolymers and copolymers of cyclic ethers such as    polyalkylene glycols, polyethylene oxide, polypropylene oxide or    copolymers thereof with bisglycidyl ethers.    13. Polyacetals such as polyoxymethylene and those polyoxymethylenes    which contain ethylene oxide as a comonomer; polyacetals modified    with thermoplastic polyurethanes, acrylates or MBS.    14. Polyphenylene oxides and sulfides, and mixtures of polyphenylene    oxides with styrene polymers or polyamides.    15. Polyurethanes derived from hydroxyl-terminated polyethers,    polyesters or polybutadienes on the one hand and aliphatic or    aromatic polyisocyanates on the other, as well as precursors    thereof.    16. Polyamides and copolyamides derived from diamines and    dicarboxylic acids and/or from aminocarboxylic acids or the    corresponding lactams, for example polyamide 4, polyamide 6,    polyamide 6/6, 6/10, 6/9, 6/12, 4/6, 12/12, polyamide 11, polyamide    12, aromatic polyamides starting from m-xylene diamine and adipic    acid; polyamides prepared from hexamethylenediamine and isophthalic    or/and terephthalic acid and with or without an elastomer as    modifier, for example poly-2,4,4,-trimethylhexamethylene    terephthalamide or poly-mphenylene isophthalamide; and also block    copolymers of the aforementioned polyamides with polyolefins, olefin    copolymers, ionomers or chemically bonded or grafted elastomers; or    with polyethers, e.g. with polyethylene glycol, polypropylene glycol    or polytetramethylene glycol; as well as polyamides or copolyamides    modified with EPDM or ABS; and polyamides condensed during    processing (RIM polyamide systems).    17. Polyureas, polyimides, polyamide-imides, polyetherimids,    polyesterimids, polyhydantoins and polybenzimidazoles.    18. Polyesters derived from dicarboxylic acids and diols and/or from    hydroxycarboxylic acids or the corresponding lactones, for example    polyethylene terephthalate, polybutylene terephthalate,    poly-1,4-dimethylolcyclohexane terephthalate, polyalkylene    naphthalate (PAN) and polyhydroxybenzoates, as well as block    copolyether esters derived from hydroxyl-terminated polyethers; and    also polyesters modified with polycarbonates or MBS.    19. Polycarbonates and polyester carbonates.    20. Polyketones.    21. Polysulfones, polyether sulfones and polyether ketones.    22. Blends of the aforementioned polymers (polyblends), for example    PP/EPDM, Polyamide/EPDM or ABS, PVC/EVA, PVC/ABS, PVC/MBS, PC/ABS,    PBTP/ABS, PC/ASA, PC/PBT, PVC/CPE, PVC/acrylates, POM/thermoplastic    PUR, PC/thermoplastic PUR, POM/acrylate, POM/MBS, PPO/HIPS, PPO/PA    6.6 and copolymers, PA/HDPE, PA/PP, PA/PPO, PBT/PC/ABS or    PBT/PET/PC.    Sterically Hindered Amine Stabilizers of Component (i)

The present hindered amines are for example monomeric compounds or areoligomeric or polymeric compounds.

The present sterically hindered amine stabilizers of component (i) areknown in the art, and are for example of the formula

where

G₁ and G₂ are independently alkyl of 1 to 8 carbon atoms or are togetherpentamethylene,

Z₁ and Z₂ are each methyl, or Z₁ and Z₂ together form a linking moietywhich may additionally be substituted by an ester, ether, amide, amino,carboxy or urethane group, and

E is oxyl, hydroxyl, alkoxy, cycloalkoxy, aralkoxy, aryloxy, —O—CO—OZ₃,—O—Si(Z₄)₃, —O—PO(OZ₅)₂ or —O—CH₂—OZ where Z₃, Z₄, Z₅ and Z are selectedfrom the group consisting of hydrogen, an aliphatic, araliphatic andaromatic moiety; or E is —O-T-(OH)_(b),

T is a straight or branched chain alkylene of 1 to 18 carbon atoms,cycloalkylene of 5 to 18 carbon atoms, cycloalkenylene of 5 to 18 carbonatoms, a straight or branched chain alkylene of 1 to 4 carbon atomssubstituted by phenyl or by phenyl substituted by one or two alkylgroups of 1 to 4 carbon atoms;

b is 1, 2 or 3 with the proviso that b cannot exceed the number ofcarbon atoms in T, and when b is 2 or 3, each hydroxyl group is attachedto a different carbon atoms of T.

E is for example oxyl, hydroxyl, alkoxy, cycloalkoxy or aralkoxy. Forinstance, E is methoxy, propoxy, cyclohexyloxy or octyloxy.

The present sterically hindered amine stabilizers of component (i) arefor example of the formula A-R

wherein

E is oxyl, hydroxyl, alkoxy of 1 to 18 carbon atoms, cycloalkoxy of 5 to12 carbon atoms or aralkoxy of 7 to 15 carbon atoms, or E is—O-T-(OH)_(b),

T is a straight or branched chain alkylene of 1 to 18 carbon atoms,cycloalkylene of 5 to 18 carbon atoms, cycloalkenylene of 5 to 18 carbonatoms, a straight or branched chain alkylene of 1 to 4 carbon atomssubstituted by phenyl or by phenyl substituted by one or two alkylgroups of 1 to 4 carbon atoms;

b is 1, 2 or 3 with the proviso that b cannot exceed the number ofcarbon atoms in T, and when b is 2 or 3, each hydroxyl group is attachedto a different carbon atoms of T;

R is hydrogen or methyl,

m is 1 to 4,

when m is 1,

R₂ is hydrogen, C₁–C₁₈alkyl or said alkyl optionally interrupted by oneor more oxygen atoms, C₂–C₁₂alkenyl, C₆–C₁₀aryl, C₇–C₁₈aralkyl,glycidyl, a monovalent acyl radical of an aliphatic, cycloaliphatic oraromatic carboxylic acid, or a carbamic acid, for example an acylradical of an aliphatic carboxylic acid having 2–18 C atoms, of acycloaliphatic carboxylic acid having 5–12 C atoms or of an aromaticcarboxylic acid having 7–15 C atoms, or

wherein x is 0 or 1,

wherein y is 2–4;

when m is 2,

R₂ is C₁–C₁₂alkylene, C₄–C₁₂alkenylene, xylylene, a divalent acylradical of an aliphatic, cycloaliphatic, araliphatic or aromaticdicarboxylic acid or of a dicarbamic acid, for example an acyl radicalof an aliphatic dicarboxylic acid having 2–18 C atoms, of acycloaliphatic or aromatic dicarboxylic acid having 8–14 C atoms, or ofan aliphatic, cycloaliphatic or aromatic dicarbamic acid having 8–14 Catoms;

wherein D₁ and D₂ are independently hydrogen, an alkyl radicalcontaining up to 8 carbon atoms, an aryl or aralkyl radical including3,5-di-t-butyl-4-hydroxybenzyl radical, D₃ is hydrogen, or an alkyl oralkenyl radical containing up to 18 carbon atoms, and d is 0–20;

when m is 3, R₂ is a trivalent acyl radical of an aliphatic, unsaturatedaliphatic, cycloaliphatic, or aromatic tricarboxylic acid;

when m is 4, R₂ is a tetravalent acyl radical of a saturated orunsaturated aliphatic or aromatic tetracarboxylic acid including1,2,3,4-butanetetracarboxylic acid, 1,2,3,4-but-2-enetetracarboxylic,and 1,2,3,5- and 1,2,4,5-pentanetetracarboxylic acid;

p is 1, 2 or 3,

R₃ is hydrogen, C₁–C₁₂alkyl, C₅–C₇cycloalkyl, C₇–C₉aralkyl,C₂–C₁₈alkanoyl, C₃–C₅alkenoyl or benzoyl;

when p is 1,

R₄ is hydrogen, C₁–C₁₈alkyl, C₅–C₇cycloalkyl, C₂–C₈alkenyl,unsubstituted or substituted by a cyano, carbonyl or carbamide group,aryl, aralkyl, or it is glycidyl, a group of the formula —CH₂—CH(OH)-Zor of the formula —CO-Z or —CONH-Z wherein Z is hydrogen, methyl orphenyl; or a group of the formulae

where h is 0 or 1,

R₃ and R₄ together, when p is 1, can be alkylene of 4 to 6 carbon atomsor 2-oxo-polyalkylene the cyclic acyl radical of an aliphatic oraromatic 1,2- or 1,3-dicarboxylic acid,

when p is 2,

R₄ is a direct bond or is C₁–C₁₂alkylene, C₆–C₁₂arylene, xylylene, a—CH₂CH(OH)—CH₂ group or a group —CH₂—CH(OH)—CH₂—O—X—O—CH₂—CH(OH)—CH₂—wherein X is C₂–C₁₀alkylene, C₆–C₁₅arylene or C₆–C₁₂cycloalkylene; or,provided that R₃ is not alkanoyl, alkenoyl or benzoyl, R₄ can also be adivalent acyl radical of an aliphatic, cycloaliphatic or aromaticdicarboxylic acid or dicarbamic acid, or can be the group —CO—; or

R₄ is

where T₈ and T₉ are independently hydrogen, alkyl of 1 to 18 carbonatoms, or T₈ and T₉ together are alkylene of 4 to 6 carbon atoms or3-oxapentamethylene, for instance T₈ and T₉ together are3-oxapentamethylene;

when p is 3,

R₄ is 2,4,6-triazinyl,

n is 1 or 2,

when n is 1,

R₅ and R₁₅ are independently C₁–C₁₂ alkyl, C₂–C₁₂ alkenyl, C₇–C₁₂aralkyl, or R₅ is also hydrogen, or R₅ and R₁₅ together areC₂–C₈alkylene or hydroxyalkylene or C₄–C₂₂acyloxyalkylene;

when n is 2,

R₅ and R₁₅ together are (—CH₂)₂C(CH₂—)₂;

R₆ is hydrogen, C₁–C₁₂alkyl, allyl, benzyl, glycidyl orC₂–C₆alkoxyalkyl;

when n is 1,

R₇ is hydrogen, C₁–C₁₂alkyl, C₃–C₅alkenyl, C₇–Cgaralkyl,C₅–C₇cycloalkyl, C₂–C₄hydroxyalkyl, C₂–C₆alkoxyalkyl, C₆–C₁₀ aryl,glycidyl, a group of the formula —(CH₂)_(t)—COO-Q or of the formula—(CH₂)_(t)—O—CO-Q wherein t is 1 or 2, and Q is C₁–C₄alkyl or phenyl; or

when n is 2,

R₇ is C₂–C₁₂alkylene, C₆–C₁₂arylene, a group—CH₂CH(OH)—CH₂—O—X—O—CH₂—CH(OH)CH₂— wherein X is C₂–C₁₀alkylene,C₆–C₁₅arylene or C₆–C₁₂cycloalkylene, or a groupCH₂CH(OZ′)CH₂—(OCH₂—CH(OZ′)CH₂)₂— wherein Z′ is hydrogen, C₁–C₁₈alkyl,allyl, benzyl, C₂–C₁₂alkanoyl or benzoyl;

Q₁ is —N(R₈)— or —O—; E₇ is C₁–C₃ alkylene, the group —CH₂—CH(R₉)—O—wherein R₉ is hydrogen, methyl or phenyl, the group —(CH₂)₃—NH— or adirect bond;

R₁₀ is hydrogen or C₁–C₁₈ alkyl, R₈ is hydrogen, C₁–C₁₈alkyl,C₅–C₇cycloalkyl, C₇–C₁₂aralkyl, cyanoethyl, C₆–C₁₀aryl, the group—CH₂—CH(R₉)—OH wherein R₉ has the meaning defined above; a group of theformula

or a group of the formula

wherein G₄ is C₂–C₆alkylene or C₆–C₁₂arylene; or R₈ is a group-E₇–CO—NH—CH₂—OR₁₀;

Formula F denotes a recurring structural unit of a polymer where T₃ isethylene or 1,2-propylene, is the repeating structural unit derived froman alpha-olefin copolymer with an alkyl acrylate or methacrylate; forexample a copolymer of ethylene and ethyl acrylate, and where k is 2 to100;

T₄ has the same meaning as R₄ when p is 1 or 2,

T₅ is methyl,

T₆ is methyl or ethyl, or T₅ and T₆ together are tetramethylene orpentamethylene, for instance T₅ and T₆ are each methyl,

M and Y are independently methylene or carbonyl, and T₄ is ethylenewhere n is 2;

T₇ is the same as R₇, and T₇ is for example octamethylene where n is 2,

T₁₀ and T₁₁ are independently alkylene of 2 to 12 carbon atoms, or T₁₁is

T₁₂ is piperazinyl,

where R₁₁ is the same as R₃ or is also

a, b and c are independently 2 or 3, and f is 0 or 1, for instance a andc are each 3, b is 2 and f is 1; and

e is 2, 3 or 4, for example 4;

T₁₃ is the same as R₂ with the proviso that T₁₃ cannot be hydrogen whenn is 1;

E₁ and E₂, being different, each are —CO— or —N(E₅)— where E₅ ishydrogen, C₁–C₁₂ alkyl or C₄–C₂₂ alkoxycarbonylalkyl, for instance E₁ is—CO— and E₂ is —N(E₅)—,

E₃ is hydrogen, alkyl of 1 to 30 carbon atoms, phenyl, naphthyl, saidphenyl or said naphthyl substituted by chlorine or by alkyl of 1 to 4carbon atoms, or phenylalkyl of 7 to 12 carbon atoms, or saidphenylalkyl substituted by alkyl of 1 to 4 carbon atoms,

E₄ is hydrogen, alkyl of 1 to 30 carbon atoms, phenyl, naphthyl orphenylalkyl of 7 to 12 carbon atoms, or

E₃ and E₄ together are polymethylene of 4 to 17 carbon atoms, or saidpolymethylene substituted by up to four alkyl groups of 1 to 4 carbonatoms, for example methyl,

E₆ is an aliphatic or aromatic tetravalent radical, R₂ of formula (N) isa previously defined when m is 1;

G₁ a direct bond, C₁–C₁₂ alkylene, phenylene or —NH-G′-NH wherein G′ isC₁–C₁₂ alkylene; or

wherein the hindered amine compound is a compound of the formula I, II,III, IV, V, VI, VII, VIII, IX, X or XI

wherein

E₁, E₂, E₃ and E₄ are independently alkyl of 1 to 4 carbon atoms, or E₁and E₂ are independently alkyl of 1 to 4 carbon atoms and E₃ and E₄taken together are pentamethylene, or E₁ and E₂; and E₃ and E₄ eachtaken together are pentamethylene,

R₁ is alkyl of 1 to 18 carbon atoms, cycloalkyl of 5 to 12 carbon atoms,a bicyclic or tricyclic hydrocarbon radical of 7 to 12 carbon atoms,phenylalkyl of 7 to 15 carbon atoms, aryl of 6 to 10 carbon atoms orsaid aryl substituted by one to three alkyl of 1 to 8 carbon atoms,

R₂ is hydrogen or a linear or branched chain alkyl of 1 to 12 carbonatoms,

R₃ is alkylene of 1 to 8 carbon atoms, or R₃ is —CO—, —CO—R₄—, —CONR₂—,or —CO—NR₂—R₄—,

R₄ is alkylene of 1 to 8 carbon atoms,

R₅ is hydrogen, a linear or branched chain alkyl of 1 to 12 carbonatoms, or

or when R₄ is ethylene, two R₅ methyl substituents can be linked by adirect bond so that the triazine bridging group —N(R₅)—R₄—N(R₅)— is apiperazin-1,4-diyl moiety,

R₆ is alkylene of 2 to 8 carbon atoms or R₆ is

with the proviso that Y is not —OH when R₆ is the structure depictedabove,

A is —O— or —NR₇— where R₇ is hydrogen, a straight or branched chainalkyl of 1 to 12 carbon atoms, or R₇ is

T is phenoxy, phenoxy substituted by one or two alkyl groups of 1 to 4carbon atoms, alkoxy of 1 to 8 carbon atoms or —N(R₂)₂ with thestipulation that R₂ is not hydrogen, or T is

X is —NH₂, —NCO, —OH, —O-glycidyl, or —NHNH₂, and

Y is —OH, —NH₂, —NHR₂ where R₂ is not hydrogen; or Y is —NCO, —COOH,oxiranyl, —O—glycidyl, or —Si(OR₂)₃; or the combination R₃—Y— is—CH₂CH(OH)R₂ where R₂ is alkyl or said alkyl interrupted by one to fouroxygen atoms, or R₃—Y— is —CH₂OR₂;

or

wherein the hindered amine compound is a mixture ofN,N′,N′″-tris{2,4-bis[(1-hydrocarbyloxy-2,2,6,6-tetramethylpiperidin-4-yl)alkylamino]-s-triazin-6-yl}-3,3′-ethylenediiminodipropylamine;N,N′,N″-tris{2,4-bis[(1-hydrocarbyloxy-2,2,6,6-tetramethylpiperidin-4-yl)alkylamino]-s-triazin-6-yl}-3,3′-ethylenediiminodipropylamine,and bridged derivatives as described by formulas I, II, IIA and IIIR₁NH—CH₂CH₂CH₂NR₂CH₂CH₂NR₃CH₂CH₂CH₂NHR₄  (I)T-E₁-T₁  (II)T-E₁  (IIA)G-E₁-G₁-E₁-G₂  (III)where in the tetraamine of formula I

R₁ and R₂ are the s-triazine moiety E; and one of R₃ and R₄ is thes-triazine moiety E with the other of R₃ or R₄ being hydrogen,

E is

R is methyl, propyl, cyclohexyl or octyl, for instance cyclohexyl,

R₅ is alkyl of 1 to 12 carbon atoms, for example n-butyl,

where in the compound of formula II or IIA when R is propyl, cyclohexylor octyl,

T and T₁ are each a tetraamine substituted by R₁—R₄ as is defined forformula I, where

(1) one of the s-triazine moieties E in each tetraamine is replaced bythe group E₁ which forms a bridge between two tetraamines T and T₁,

E₁ is

or

(2) the group E₁ can have both termini in the same tetraamine T as informula IIA where two of the E moieties of the tetraamine are replacedby one E₁ group, or

(3) all three s-triazine substituents of tetraamine T can be E₁ suchthat one E₁ links T and T₁ and a second E₁ has both termini intetraamine T,

L is propanediyl, cyclohexanediyl or octanediyl;

where in the compound of formula III

G, G₁ and G₂ are each tetraamines substituted by R₁—R₄ as defined forformula I, except that G and G₂ each have one of the s-triazine moietiesE replaced by E₁, and G₁ has two of the triazine moieties E replaced byE₁, so that there is a bridge between G and G₁ and a second bridgebetween G₁ and G₂;

which mixture is prepared by reacting two to four equivalents of2,4-bis[(1-hydrocarbyl-oxy-2,2,6,6-etramethylpiperidin-4-yl)butylamino]-6-chloro-s-triazinewith one equivalent of N,N′-bis(3-aminopropyl)ethylenediamine;

or the hindered amine is a compound of the formula IIIb

in which the index n ranges from 1 to 15;

R₁₂ is C₂–C₁₂alkylene, C₄–C₁₂alkenylene, C₅–C₇cycloalkylene,C₅–C₇cycloalkylene-di(C₁–C₄alkylene),C₁–C₄alkylenedi(C₅–C₇cycloalkylene), phenylenedi(C₁–C₄alkylene) orC₄–C₁₂alkylene interrupted by 1,4-piperazinediyl, —O— or >N—X₁ with X₁being C₁–C₁₂acyl or (C₁–C₁₂alkoxy)carbonyl or having one of thedefinitions of R₁₄ given below except hydrogen; or R₁₂ is a group of theformula (Ib′) or (Ic′);

with m being 2 or 3,

X₂ being C₁–C₁₈alkyl, C₅–C₁₂cycloalkyl which is unsubstituted orsubstituted by 1, 2 or 3 C₁–C₄alkyl; phenyl which is unsubstituted orsubstituted by 1, 2 or 3 C₁–C₄alkyl or C₁–C₄alkoxy; C₇–C₉ phenylalkylwhich is unsubstituted or substituted on the phenyl by 1, 2 or 3C₁–C₄alkyl; and

the radicals X₃ being independently of one another C₂–C₁₂alkylene;

R₁₃, R₁₄ and R₁₅, which are identical or different, are hydrogen,C₁–C₁₈alkyl, C₅–C₁₂cycloalkyl which is unsubstituted or substituted by1, 2 or 3 C₁–C₄alkyl; C₃–C₁₈alkenyl, phenyl which is unsubstituted orsubstituted by 1, 2 or 3 C₁–C₄alkyl or C₁–C₄alkoxy; C₇–C₉phenylalkylwhich is unsubstituted or substituted on the phenyl by 1, 2 or 3C₁–C₄alkyl; tetrahydrofurfuryl or C₂–C₄alkyl which is substituted in the2, 3 or 4 position by —OH, C₁–C₈alkoxy, di(C₁–C₄alkyl)amino or a groupof the formula (Ie′);

with Y being —O—, —CH₂—, —CH₂CH₂— or >N—CH₃,

or —N(R₁₄)(R₁₅) is additionally a group of the formula (Ie′);

the radicals A are independently of one another —OR₁₃, —N(R₁₄)(R₁₅) or agroup of the formula (IIId);

X is —O— or >N—R₁₆;

R₁₆ is hydrogen, C₁–C₁₈alkyl, C₃–C₁₈alkenyl, C₅–C₁₂cycloalkyl which isunsubstituted or substituted by 1, 2 or 3 C₁–C₄alkyl; C₇–C₉phenylalkylwhich is unsubstituted or substituted on the phenyl by 1, 2 or 3C₁–C₄alkyl; tetrahydrofurfuryl, a group of the formula (IIIf),

or C₂–C₄alkyl which is substituted in the 2, 3 or 4 position by —OH,C₁–C₈alkoxy, di(C₁–C₄alkyl)amino or a group of the formula (Ie′);

R₁₁ has one of the definitions given for R₁₆; and

the radicals B have independently of one another one of the definitionsgiven for A.

Alkyl is straight or branched and is for example methyl, ethyl,n-propyl, n-butyl, sec-butyl, tert-butyl, n-hexyl, n-octyl,2-ethylhexyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl,n-tetradecyl, n-hexadecyl or n-octadecyl.

Cycloalkyl groups include cyclopentyl and cyclohexyl; typicalcycloalkenyl groups include cyclohexenyl; while typical aralkyl groupsinclude benzyl, alpha-methyl-benzyl, alpha,alphadimethylbenzyl orphenethyl.

If R₂ is a monovalent acyl radical of a carboxylic acid, it is forexample an acyl radical of acetic acid, stearic acid, salicyclic acid,benzoic acid or β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid.

If R₂ is a divalent acyl radical of a dicarboxylic acid, it is forexample an acyl radical of oxalic acid, adipic acid, succinic acid,suberic acid, sebacic acid, phthalic acid dibutylmalonic acid,dibenzylmalonic acid orbutyl-(3,5-di-tert-butyl-4-hydropxybenzyl)-malonic acid, orbicycloheptenedicarboxylic acid, with succinates, sebacates, phthalatesand isophthalates being specific examples.

If R₂ is a divalent acyl radical of a dicarbamic acid, it is for examplean acyl radical of hexamethylenedicarbamic acid or of2,4-toluylenedicarbamic acid.

Hindered alkoxyamine stabilizers of component (i) are well known in theart, also known as N-alkoxy hindered amines and NOR hindered amines orNOR hindered amine light stabilizers or NOR HALS.

They are disclosed for example in U.S. Pat. Nos. 5,004,770, 5,204,473,5,096,950, 5,300,544, 5,112,890, 5,124,378, 5,145,893, 5,216,156,5,844,026, 6,117,995, 6,271,377, and U.S. application Ser. No.09/505,529, filed Feb. 17, 2000, Ser. No. 09/794,710, filed Feb. 27,2001, Ser. No. 09/714,717, filed Nov. 16, 2000, Ser. No. 09/502,239,filed Nov. 3, 1999 and 60/312,517, filed Aug. 15, 2001. The relevantdisclosures of these patents and applications are hereby incorporated byreference.

U.S. Pat. No. 6,271,377, and U.S. application Ser. No. 09/505,529, filedFeb. 17, 2000, and Ser. No. 09/794,710, filed Feb. 27, 2001, cited abovedisclose hindered hydroxyalkoxyamine stabilizers. For the purposes ofthis invention, the hindered hydoxyalkoxyamine stabilizers areconsidered a subset of the hindered alkoxyamine stabilizers and are partof present component (i). Hindered hydroxyalkoxyamine stabilizers arealso known as N-hydroxyalkoxy hindered amines, or NORol HALS.

Suitable hindered amines of component (i) include for example:

NOR1 1-cyclohexyloxy-2,2,6,6-tetramethyl-4-octadecylaminopiperidine;

NOR2 bis(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl)sebacate;

NOR32,4-bis[(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)butylamino]-6-(2-hydroxyethylamino-s-triazine;

NOR42,4-bis[(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)butylamino]-6-chloro-s-triazine;

NOR51-(2-hydroxy-2-methylpropoxy)-4-hydroxy-2,2,6,6-tetramethylpiperidine;

NOR6 1-(2-hydroxy-2-methylpropoxy)-4-oxo-2,2,6,6-tetramethylpiperidine;

NOR71-(2-hydroxy-2-methylpropoxy)-4-octadecanoyloxy-2,2,6,6-tetramethylpiperidine;

NOR8bis(1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl)sebacate;

NOR9bis(1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl)adipate;

NOR102,4-bis{N-[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl]-N-butylamino}-6-(2-hydroxyethylamino)-s-triazine;

NOR11 the reaction product of2,4-bis[(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)butylamino]-6-chloro-s-triazinewith N,N′-bis(3-aminopropyl)ethylenediamine) [CAS Reg. No. 191680-81-6];

NOR12 the compound of formula

in which n is from 1 to 15; and

NOR13 bis(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)adipate.

Compound NOR12 is disclosed in example 2 of U.S. Pat. No. 6,117,995.

The stabilizers of component (i) are advantageously contained in thecomposition of the invention in an amount from about 0.05% to about 20%by weight based on the polymer substrate (a); for example from about0.1% to about 10% by weight; for example from about 0.2% to about 8% byweight; for instance from about 0.5% to about 3% by weight. For example,the stabilizers of component (i) are present from about 0.05% to about15%, from about 0.05% to about 10%, from about 0.05% to about 8%, fromabout 0.05% to about 5% or from about 0.05% to about 3% by weight basedon the weight of substrate (a). For example, the stabilizers ofcomponent (i) are present from about 0.1% to about 20%, from about 0.2to about 20%, from about 0.5 to about 20% or from about 1% to about 20%by weight based on the weight of substrate (a).

Conventional Flame Retardants of Component (ii)

Oganohalogen flame retardants are for example:

Chloroalkyl phosphate esters (ANTIBLAZE® AB-100, Albright & Wilson;FYROL® FR-2, Akzo Nobel),

tris(2-chloroethyl)phosphate

polybrominated diphenyl oxide (DE-60F, Great Lakes Corp.),

decabromodiphenyl oxide (DBDPO; SAYTEX® 102E),

tris[3-bromo-2,2-bis(bromomethyl)propyl]phosphate (PB 370®, FMC Corp.),

tris(2,3-dibromopropyl)phosphate

tris(2,3-dichloropropyl)phosphate,

chlorendic acid,

tetrachlorophthalic acid,

tetrabromophthalic acid,

bis-(N,N′-hydroxyethyl)tetrachlorphenylene diamine,

poly-β-chloroethyl triphosponate mixture

bis(2,3-dibromopropyl ether) of tetrabromobisphenol A (PE68),

brominated epoxy resin,

ethylene-bis(tetrabromophthalimide) (SAYTEX® BT-93),

bis(hexachlorocyclopentadieno)cyclooctane (DECLORANE PLUS®),

chlorinated paraffins,

octabromodiphenyl ether,

hexachlorocyclopentadiene derivatives,

1,2-bis(tribromophenoxy)ethane (FF680),

tetrabromo-bisphenol A (SAYTEX® RB100),

ethylene bis-(dibromo-norbornanedicarboximide) (SAYTEX® BN-451),

bis-(hexachlorocyclopentadieno)cyclooctane,

PTFE

tris-(2,3-dibromopropyl)-isocyanurate, and

ethylene-bis-tetrabromophthalimide.

The phosphorus containing flame retardants are for example:

Tetraphenyl resorcinol diphosphite (FYROLFLEX® RDP, Akzo Nobel),

triphenyl phosphate,

trioctyl phosphate,

tricresyl phosphate,

tetrakis(hydroxymethyl)phosphonium sulfide,

diethyl-N,N-bis(2-hydroxyethyl)-aminomethyl phosphonate,

hydroxyalkyl esters of phosphorus acids,

ammonium polyphosphate (APP) or (HOSTAFLAM® AP750),

resorcinol diphosphate oligomer (RDP),

phosphazene flame retardants and

ethylenediamine diphosphate (EDAP).

Isocyanurate flame retardants include polyisocyanurate, esters ofisocyanuric acid and isocyanurates. For example, an hydroxyalkylisocyanurate such as tris-(2-hydroxyethyl)isocyanurate,tris(hydroxymethyl)isocyanurate, tris(3-hydroxy-n-proyl)isocyanurate ortriglycidyl isocyanurate.

The melamine based flame retardants are for example:

melamine cyanurate,

melamine borate,

melamine phosphates,

melamine polyphosphates and

melamine pyrophosphates.

Boric acid may be included as a flame retardant.

The halogenated flame retardants useful in the present invention may beselected from organic aromatic halogenated compounds such as halogenatedbenzenes, biphenyls, phenols, ethers or esters thereof, bisphenols,diphenyloxides, aromatic carboxylic acids or polyacids, anhydrides,amides or imides thereof; organic cycloaliphatic or polycycloaliphatichalogenated compounds; and organic aliphatic halogenated compounds suchas halogenated paraffins, oligo- or polymers, alkylphosphates oralkylisocyanurates. These components are largely known in the art, seee.g. U.S. Pat. No. 4,579,906 (e.g. col. 3, lines 30–41), U.S. Pat. No.5,393,812; see also Plastics Additives Handbook, Ed. by H. Zweifel,5^(th) Ed., Hanser Publ., Munich 2001, pp. 681–698.

The phosphazene flame retardants are well known in the art. They aredisclosed for example in EP1104766, JP07292233, DE19828541, DE1988536,JP11263885, U.S. Pat. Nos. 4,107,108, 4,108,805 and 4,079,035 and6,265,599. The relevant disclosures of the U.S. Patents are herebyincorporated by reference.

PTFE, polytetrafluoroethylene (for example Teflon® 6C; E. I. Du Pont),may be advantageously added to the present compositions as an additionalflame retardant, as disclosed in U.S. application 60/312,517, filed Aug.15, 2001.

Component (ii) is advantageously contained in the composition of theinvention in an amount from about 0.5% to about 45% by weight of thepolymeric substrate (a); for instance about 3% to about 40%; for exampleabout 5% to about 35% by weight of component (a). For example, component(ii) is employed from about 0.5% to about 10% by weight, from about 1%to about 10%, from about 3% to about 10% or from about 5% to about 10%by weight, based on the weight of the polymeric substrate. For example,component (ii) is employed from about 0.5% to about 8%, from about 0.5%to about 6%, from about 0.5% to about 5%, or from about 0.5% to about 3%by weight, based on the weight of the polymeric substrate.

The ratio (parts by weight) of component (i) to component (ii) is forexample between about 1:5 to about 1:200, for instance from about 1:50to about 1:100, or about 1:10 to about 1:25. For example the ratio ofcomponent (i) to component (ii) is from about 1:10 to about 1:200, fromabout 1:25 to about 1:200, from about 1:50 to about 1:200 or from about1:100 to about 1:200. For example, the weight ratio of component (i) tocomponent (ii) is from about 1:5 to about 1:100, from about 1:5 to about1:50, from about 1:5 to about 1:25, or from about 1:5 to about 1:10.

The amount of component (ii) used also depends on the effectiveness ofthe specific compound(s), the polymer and the specific application type.

Acid Scavengers of Component (iii)

Acid scavengers are for example hydrotalcites and amorphous basicaluminum magnesium carbonates, such as those described in U.S. Pat. Nos.4,427,816, 5,106,898 and 5,234,981, the relevant disclosures of whichare hereby incorporated by reference. Hydrotalcite is also known ashycite or DHT4A.

Hydrotalcites are natural or synthetic. The natural hydrotalcite is heldto possess a structure Mg₆Al₂(OH)₁₆CO₃.4H₂O.

A typical empirical formula of a synthetic hydrotalcite isAl₂Mg_(4.35)OH_(11.36)CO_(3(1.67)).xH₂O.

Examples of the synthetic product include:Mg_(0.7)Al_(0.3)(OH)₂(CO₃)_(0.15).0.54H₂O, Mg_(4.5)Al₂(OH)₁₃CO₃.3.5H₂Oand Mg_(4.2)Al(OH)_(12.4)CO₃.

The acid scavengers are present in the polymeric compositions at a levelof about 0.1% to about 1.0% by weight, based on the weight of component(a). For instance, the present acid scavengers are present from about0.2% to about to about 0.8% or from about 0.4% to about 0.6% by weight,based on the weight of component (a). For example, the present acidscavengers are present from about 0.1% to about 0.8%, from about 0.1% toabout 0.6%, from about 0.1% to about 0.4% or from about 0.1% to about0.2% by weight based on the weight of component (a). For instance, thepresent acid scavengers are present from about 0.2% to about 1.0%, fromabout 0.4% to about 1.0%, from about 0.6% to about 1.0% or from about0.8% to about 1.0% by weight based on the weight of component (a).

The acid scavengers aid the present compositions in color, odor andstability.

The compositions of the present invention are useful for manyapplications, for example outdoor applications, including the following:

-   Thermoplastic olefins-   Paintable thermoplastic olefins-   Polypropylene molded articles-   Polyethylene film-   Thermoplastic elastomers with other costabilizers-   Grease-filled wire and cable insulation-   Coatings-   Coatings over plastic substrates-   Polyolefin tanks or containers containing chemicals-   Polyolefin films with an antifog agent-   Polyolefin films with IR thermal fillers such as hydrotalcites, e.g.    DHT4A-   Polyolefin films with an antistatic agent-   Flame-resistant molded polypropylene articles-   Flame-resistant molded thermoplastic olefins-   Flame-resistant polyethylene film-   Pre-formed films for lamination to plastic substrates-   Electronic appliances-   Containers, boxes, bins for storage and transportation-   Automotive applications e.g. dashboard, back board-   Furniture e.g. stadium seats, public seats-   Roofing sheets-   Roofing membranes-   Flooring materials-   Liners-   Profiles, for example window and door profiles-   Geomembranes-   Awning fabrics-   Banner films-   Upholstery-   Drapery-   Carpeting-   Tents, tarpaulins-   Surgical gowns, caps and other hospital applications-   Fabrics-   Ropes-   Nets-   Tire cords-   Parachutes

The compositions of the present invention are useful in textilelaminates and as coatings of substrates as described in U.S. Pat. Nos.6,235,658 and 6,251,995, the relevant disclosures of which are herebyincorporated by reference.

The materials containing the stabilizers described herein can be usedfor the production of moldings, rotomolded articles, injection moldedarticles, blow molded articles, mono- and multilayer films, extrudedprofiles, surface coatings and the like.

The resulting stabilized compositions of the invention may optionallyalso contain various conventional additives, for example in amounts fromabout 0.01 to about 10%, for instance from about 0.025 to about 4%, forexample from about 0.1 to about 2% by weight of component (a), such asthe materials listed below, or mixtures thereof.

1. Antioxidants

1.1. Alkylated monophenols, for example2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-dimethylphenol,2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-n-butylphenol,2,6-di-tert-butyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol,2-(α-methylcyclohexyl)-4,6-dimethylphenol,2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol,2,6-di-tert-butyl-4-methoxymethylphenol, nonylphenols which are linearor branched in the side chains, for example,2,6-di-nonyl-4-methylphenol,2,4-dimethyl-6-(1′-methylundec-1′-yl)phenol,2,4-dimethyl-6-(1′-methylheptadec-1′-yl)phenol,2,4-dimethyl-6-(1′-methyltridec-1′-yl)phenol and mixtures thereof.1.2. Alkylthiomethylphenols, for example2,4-dioctylthiomethyl-6-tert-butylphenol,2,4-dioctylthiomethyl-6-methylphenol,2,4-dioctylthiomethyl-6-ethylphenol,2,6-di-dodecylthiomethyl-4-nonylphenol.1.3. Hydroquinones and alkylated hydroquinones, for example2,6-di-tert-butyl-4-methoxyphenol, 2,5-di-tert-butylhydroquinone,2,5-di-tert-amylhydroquinone, 2,6-diphenyl-4-octadecyloxyphenol,2,6-di-tert-butylhydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole,3,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyphenylstearate, bis-(3,5-di-tert-butyl-4-hydroxyphenyl)adipate.1.4. Tocopherols, for example α-tocopherol, β-tocopherol, γ-tocopherol,δ-tocopherol and mixtures thereof (Vitamin E).1.5. Hydroxylated thiodiphenyl ethers, for example2,2′-thiobis(6-tert-butyl-4-methylphenol), 2,2′-thiobis(4-octylphenol),4,4′-thiobis(6-tert-butyl-3-methylphenol),4,4′-thiobis(6-tert-butyl-2-methylphenol),4,4′-thiobis-(3,6-di-sec-amylphenol),4,4′-bis(2,6-dimethyl-4-hydroxyphenyl)disulfide.1.6. Alkylidenebisphenols, for example2,2′-methylenebis(6-tert-butyl-4-methylphenol),2,2′-methylenebis(6-tert-butyl-4-ethylphenol),2,2′-methylenebis[4-methyl-6-(α-methylcyclohexyl)-phenol],2,2′-methylenebis(4-methyl-6-cyclohexylphenol),2,2′-methylenebis(6-nonyl-4-methylphenol),2,2′-methylenebis(4,6-di-tert-butylphenol),2,2′-ethylidenebis(4,6-di-tert-butylphenol),2,2′-ethylidenebis(6-tert-butyl-4-isobutylphenol),2,2′-methylenebis[6-(α-methylbenzyl)-4-nonylphenol],2,2′-methylenebis[6-(α,α-dimethylbenzyl)-4-nonylphenol],4,4′-methylenebis(2,6-di-tert-butylphenol),4,4′-methylenebis(6-tert-butyl-2-methylphenol),1,1-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)butane,2,6-bis(3-tert-butyl-5-methyl-2-hydroxybenzyl)-4-methylphenol,1,1,3-tris(5-tert-butyl-4-hydroxy-2-methylphenyl)butane,1,1-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)-3-n-dodecylmercaptobutane,ethylene glycol bis[3,3-bis(3′-tert-butyl-4′-hydroxyphenyl)butyrate],bis(3-tert-butyl-4-hydroxy-5-methyl-phenyl)dicyclopentadiene,bis[2-(3′-tert-butyl-2′-hydroxy-5′-methylbenzyl)-6-tert-butyl-4-methylphenyl]terephthalate,1,1-bis-(3,5-dimethyl-2-hydroxyphenyl)butane,2,2-bis-(3,5-di-tert-butyl-4-hydroxyphenyl)propane,2,2-bis-(5-tert-butyl-4-hydroxy2-methylphenyl)-4-n-dodecylmercaptobutane,1,1,5,5-tetra-(5-tert-butyl-4-hydroxy-2-methylphenyl)pentane.1.7. O-, N- and S-benzyl compounds, for example3,5,3′,5′-tetra-tert-butyl-4,4′-dihydroxydibenzyl ether,octadecyl-4-hydroxy-3,5-dimethylbenzylmercaptoacetate,tridecyl-4-hydroxy-3,5-di-tert-butylbenzylmercaptoacetate,tris(3,5-di-tert-butyl-4-hydroxybenzyl)amine,bis(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)dithioterephthalate,bis(3,5-di-tert-butyl-4-hydroxybenzyl)sulfide,isooctyl-3,5-di-tert-butyl-4-hydroxybenzylmercaptoacetate.1.8. Hydroxybenzylated malonates, for exampledioctadecyl-2,2-bis-(3,5-di-tert-butyl-2-hydroxybenzyl)-malonate,di-octadecyl-2-(3-tert-butyl-4-hydroxy-5-methylbenzyl)-malonate,di-dodecylmercaptoethyl-2,2-bis-(3,5-di-tert-butyl-4-hydroxybenzyl)-malonate,bis[4-(1,1,3,3-tetramethylbutyl)phenyl]-2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate.1.9. Aromatic hydroxybenzyl compounds, for example1,3,5-tris-(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene,1,4-bis(3,5-di-tert-butyl-4-hydroxybenzyl)-2,3,5,6-tetramethylbenzene,2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)phenol.1.10. Triazine Compounds, for example2,4-bis(octylmercapto)-6-(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazine,2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazine,2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,3,5-triazine,2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,2,3-triazine,1,3,5-tris-(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate,1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate,2,4,6-tris-(3,5-di-tert-butyl-4-hydroxyphenylethyl)-1,3,5-triazine,1,3,5-tris(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hexahydro-1,3,5-triazine,1,3,5-tris(3,5-dicyclohexyl-4-hydroxybenzyl)isocyanurate.1.11. Benzylphosphonates, for exampledimethyl-2,5-di-tert-butyl-4-hydroxybenzylphosphonate,diethyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate,dioctadecyl3,5-di-tert-butyl-4-hydroxybenzylphosphonate,dioctadecyl-5-tert-butyl-4-hydroxy-3-methylbenzylphosphonate, thecalcium salt of the monoethyl ester of3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid.1.12. Acylaminophenols, for example 4-hydroxylauranilide,4-hydroxystearanilide, octylN-(3,5-di-tert-butyl-4-hydroxyphenyl)carbamate.1.13. Esters of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid withmono- or polyhydric alcohols, e.g. with methanol, ethanol, n-octanol,i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol,1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethyleneglycol, triethylene glycol, pentaerythritol,tris(hydroxyethyl)isocyanurate, N,N′-bis(hydroxyethyl)oxamide,3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,trimethylolpropane,4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.1.14. Esters of β-(5-tert-butyl-4-hydroxy-3-methylphenyl)propionic acidwith mono- or polyhydric alcohols, e.g. with methanol, ethanol,n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol,ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethyleneglycol, diethylene glycol, triethylene glycol, pentaerythritol,tris(hydroxyethyl)isocyanurate, N,N′-bis(hydroxyethyl)oxamide,3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,trimethylolpropane,4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.1.15. Esters of β-(3,5-dicyclohexyl-4-hydroxyphenyl)propionic acid withmono- or polyhydric alcohols, e.g. with methanol, ethanol, octanol,octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol,1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethyleneglycol, triethylene glycol, pentaerythritol,tris(hydroxyethyl)isocyanurate, N,N′-bis(hydroxyethyl)oxamide,3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,trimethylolpropane,4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.1.16. Esters of 3.5-di-tert-butyl-4-hydroxyphenyl acetic acid with mono-or polyhydric alcohols, e.g. with methanol, ethanol, octanol,octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol,1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethyleneglycol, triethylene glycol, pentaerythritol,tris(hydroxyethyl)isocyanurate, N,N′-bis(hydroxyethyl)oxamide,3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,trimethylolpropane,4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.1.17. Amides of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid e.g.N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexamethylenediamide,N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)trimethylenediamide,N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazide,N,N′-bis[2-(3-[3,5-di-tert-butyl-4-hydroxyphenyl]propionyloxy)ethyl]oxamide(Naugard®XL-1 supplied by Uniroyal).1.18. Ascorbic acid (vitamin C)1.19. Aminic antioxidants, for exampleN,N′-di-isopropyl-p-phenylenediamine,N,N′-di-sec-butyl-p-phenylenediamine,N,N′-bis(1,4-dimethylpentyl)-p-phenylenediamine,N,N′-bis(1-ethyl-3-methylpentyl)-p-phenylenediamine,N,N′-bis(1-methylheptyl)-p-phenylenediamine,N,N′-dicyclohexyl-p-phenylenediamine, N,N′-diphenyl-p-phenylenediamine,N,N′-bis(2-naphthyl)-p-phenylenediamine,N-isopropyl-N′-phenyl-p-phenylenediamine,N-(1,3-dimethylbutyl)-N′-phenyl-p-phenylenediamine,N-(1-methylheptyl)-N′-phenyl-p-phenylenediamine,N-cyclohexyl-N′-phenyl-p-phenlenediamine,4-(p-toluenesulfamoyl)diphenylamine,N,N′-dimethyl-N,N′-di-sec-butyl-p-phenylenediamine, diphenylamine,N-allyidiphenylamine, 4-isopropoxydiphenylamine,N-phenyl-1-naphthylamine, N-(4-tert-octylphenyl)-1-naphthylamine,N-phenyl-2-naphthylamine, octylated diphenylamine, for examplep,p′-di-tert-octyidiphenylamine, 4-n-butylaminophenol,4-butyrylaminophenol, 4-nonanoylaminophenol, 4-dodecanoylaminophenol,4-octadecanoylaminophenol, bis(4-methoxyphenyl)amine,2,6-di-tert-butyl-4-dimethylaminomethylphenol,2,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylmethane,N,N,N′,N′-tetramethyl-4,4′-diaminodiphenylmethane,1,2-bis[(2-methylphenyl)amino]ethane, 1,2-bis(phenylamino)propane,(o-tolyl)biguanide, bis[4-(1′,3′-dimethylbutyl)phenyl]amine,tert-octylated N-phenyl-1-naphthylamine, a mixture of mono- anddialkylated tert-butyl/tert-octyldiphenylamines, a mixture of mono- anddialkylated nonyldiphenylamines, a mixture of mono- and dialkylateddodecyldiphenylamines, a mixture of mono- and dialkylatedisopropyl/isohexyldiphenylamines, a mixture of mono- und dialkylatedtert-butyldiphenylamines, 2,3-dihydro-3,3-dimethyl-4H-1,4-benzothiazine,phenothiazine, a mixture of mono- und dialkylatedtert-butyl/tert-octylphenothiazines, a mixture of mono- und dialkylatedtert-octyl-phenothiazines, N-allylphenothiazin,N,N,N′,N′-tetraphenyl-1,4-diaminobut-2-ene,N,N-bis(2,2,6,6-tetramethylpiperid-4-yl-hexamethylenediamine,bis(2,2,6,6-tetramethylpiperid-4-yl)sebacate,2,2,6,6-tetramethylpiperidin-4-one, 2,2,6,6-tetramethylpiperidin-4-ol.2. UV absorbers and light stabilizers2.1. 2-(2-Hydroxyphenyl)-2H-benzotriazoles, for example known commercialhydroxyphenyl-2H-benzotriazoles and benzotriazoles as disclosed in, U.S.Pat. Nos. 3,004,896; 3,055,896; 3,072,585; 3,074,910; 3,189,615;3,218,332; 3,230,194; 4,127,586; 4,226,763; 4,275,004; 4,278,589;4,315,848; 4,347,180; 4,383,863; 4,675,352; 4,681,905, 4,853,471;5,268,450; 5,278,314; 5,280,124; 5,319,091; 5,410,071; 5,436,349;5,516,914; 5,554,760; 5,563,242; 5,574,166; 5,607,987, 5,977,219 and6,166,218 such as 2-(2-hydroxy-5-methylphenyl)-2H-benzotriazole,2-(3,5-di-t-butyl-2-hydroxyphenyl)-2H-benzotriazole,2-(2-hydroxy-5-t-butylphenyl)-2H-benzotriazole,2-(2-hydroxy-5-t-octylphenyl)-2H-benzotriazole,5-chloro-2-(3,5-di-t-butyl-2-hydroxyphenyl)-2H-benzotriazole,5-chloro-2-(3-t-butyl-2-hydroxy-5-methylphenyl)-2H-benzotriazole,2-(3-sec-butyl-5-t-butyl-2-hydroxyphenyl)-2H-benzotriazole,2-(2-hydroxy-4-octyloxyphenyl)-2H-benzotriazole,2-(3,5-di-t-amyl-2-hydroxyphenyl)-2H-benzotriazole,2-(3,5-bis-α-cumyl-2-hydroxyphenyl)-2H-benzotriazole,2-(3-t-butyl-2-hydroxy-5-(2-(ω-hydroxy-octa-(ethyleneoxy)carbonyl-ethyl)-,phenyl)-2H-benzotriazole,2-(3-dodecyl-2-hydroxy-5-methylphenyl)-2H-benzotriazole,2-(3-t-butyl-2-hydroxy-5-(2-octyloxycarbonyl)ethylphenyl)-2H-benzotriazole,dodecylated 2-(2-hydroxy-5-methylphenyl)-2H-benzotriazole,2-(3-t-butyl-2-hydroxy-5-(2-octyloxycarbonylethyl)phenyl)-5-chloro-2H-benzotriazole,2-(3-tert-butyl-5-(2-(2-ethylhexyloxy)-carbonylethyl)-2-hydroxyphenyl)-5-chloro-2H-benzotriazole,2-(3-t-butyl-2-hydroxy-5-(2-methoxycarbonylethyl)phenyl)-5-chloro-2H-benzotriazole,2-(3-t-butyl-2-hydroxy-5-(2-methoxycarbonylethyl)phenyl)-2H-benzotriazole,2-(3-t-butyl-5-(2-(2-ethylhexyloxy)carbonylethyl)-2-hydroxyphenyl)-2H-benzotriazole,2-(3-t-butyl-2-hydroxy-5-(2-isooctyloxycarbonylethyl)phenyl-2H-benzotriazole,2,2′-methylene-bis(4-t-octyl-(6-2H-benzotriazol-2-yl)phenol),2-(2-hydroxy-3-α-cumyl-5-t-octylphenyl)-2H-benzotriazole,2-(2-hydroxy-3-t-octyl-5-α-cumylphenyl)-2H-benzotriazole,5-fluoro-2-(2-hydroxy-3,5-di-α-cumylphenyl)-2H-benzotriazole,5-chloro-2-(2-hydroxy-3,5-di-α-cumylphenyl)-2H-benzotriazole,5-chloro-2-(2-hydroxy-3-α-cumyl-5-t-octylphenyl)-2H-benzotriazole,2-(3-t-butyl-2-hydroxy-5-(2-isooctyloxycarbonylethyl)phenyl)-5-chloro-2H-benzotriazole,5-trifluoromethyl-2-(2-hydroxy-3-α-cumyl-5-t-octylphenyl)-2H-benzotriazole,5-trifluoromethyl-2-(2-hydroxy-5-t-octylphenyl)-2H-benzotriazole,5-trifluoromethyl-2-(2-hydroxy-3,5-di-t-octylphenyl)-2H-benzotriazole,methyl3-(5-trifluoromethyl-2H-benzotriazol-2-yl)-5-t-butyl-4-hydroxyhydrocinnamate,5-butylsulfonyl-2-(2-hydroxy-3-α-cumyl-5-t-octylphenyl)-2H-benzotriazole,5-trifluoromethyl-2-(2-hydroxy-3-α-cumyl-5-t-butylphenyl)-2H-benzotriazole,5-trifluoromethyl-2-(2-hydroxy-3,5-di-t-butylphenyl)-2H-benzotriazole,5-trifluoromethyl-2-(2-hydroxy-3,5-di-α-cumylphenyl)-2H-benzotriazole,5-butylsulfonyl-2-(2-hydroxy-3,5-di-t-butylphenyl)-2H-benzotriazole and5-phenylsulfonyl-2-(2-hydroxy-3,5-di-t-butylphenyl)-2H-benzotriazole.2.2. 2-Hydroxybenzophenones, for example the 4-hydroxy, 4-methoxy,4-octyloxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy, 4,2′,4′-trihydroxyand 2′-hydroxy-4,4′-dimethoxy derivatives.2.3. Esters of substituted and unsubstituted benzoic acids, as forexample 4-tert-butyl-phenyl salicylate, phenyl salicylate, octylphenylsalicylate, dibenzoyl resorcinol, bis(4-tert-butylbenzoyl)resorcinol,benzoyl resorcinol, 2,4-di-tert-butylphenyl3,5-di-tert-butyl-4-hydroxybenzoate, hexadecyl3,5-di-tert-butyl-4-hydroxybenzoate, octadecyl3,5-di-tert-butyl-4-hydroxybenzoate, 2-methyl-4,6-di-tert-butylphenyl3,5-di-tert-butyl-4-hydroxybenzoate.2.4. Acrylates, for example ethyl α-cyano-β,β-diphenylacrylate, isooctylα-cyano-β,β-diphenylacrylate, methyl α-carbomethoxycinnamate, methylα-cyano-α-methyl-p-methoxy-cinnamate, butylα-cyano-β-methyl-p-methoxy-cinnamate, methylα-carbomethoxy-p-methoxy-cinnamate andN-(β-carbomethoxy-β-cyanovinyl)-2-methylindoline.2.5. Nickel compounds, for example nickel complexes of2,2′-thio-bis-[4-(1,1,3,3-tetramethylbutyl)phenol], such as the 1:1 or1:2 complex, with or without additional ligands such as n-butylamine,triethanolamine or N-cyclohexyldiethanolamine, nickeldibutyidithiocarbamate, nickel salts of the monoalkyl esters, e.g. themethyl or ethyl ester, of 4-hydroxy-3,5-di-tert-butylbenzylphosphonicacid, nickel complexes of ketoximes, e.g. of 2-hydroxy-4-methylphenylundecylketoxime, nickel complexes of1-phenyl-4-lauroyl-5-hydroxypyrazole, with or without additionalligands.2.6. Sterically hindered amines, for examplebis(2,2,6,6-tetramethyl-4-piperidyl)sebacate,bis(2,2,6,6-tetramethyl-4-piperidyl)succinate,bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate,bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl)sebacate,bis(1,2,2,6,6-pentamethyl-4-piperidyl)n-butyl-3,5-di-tert-butyl-4-hydroxybenzylmalonate,the condensate of1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinicacid, linear or cyclic condensates ofN,N′-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and4-tert-octylamino-2,6-dichloro-1,3,5-triazine,tris(2,2,6,6-tetramethyl-4-piperidyl)nitrilotriacetate,tetrakis(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butane-tetracarboxylate,1,1′-(1,2-ethanediyl)-bis(3,3,5,5-tetramethylpiperazinone),4-benzoyl-2,2,6,6-tetramethylpiperidine,4-stearyloxy-2,2,6,6-tetramethylpiperidine,bis(1,2,2,6,6-pentamethylpiperidyl)-2-n-butyl-2-(2-hydroxy-3,5-di-tert-butylbenzyl)malonate,3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decan-2,4-dione,bis(1-octyloxy-2,2,6,6-tetramethylpiperidyl)sebacate,bis(1-octyloxy-2,2,6,6-tetramethylpiperidyl)succinate, linear or cycliccondensates ofN,N′-bis-(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and4-morpholino-2,6-dichloro-1,3,5-triazine, the condensate of2-chloro-4,6-bis(4-n-butylamino-2,2,6,6-tetramethylpiperidyl)-1,3,5-triazineand 1,2-bis(3-aminopropylamino)ethane, the condensate of2-chloro-4,6-di-(4-n-butylamino-1,2,2,6,6-pentamethylpiperidyl)-1,3,5-triazineand 1,2-bis-(3-aminopropylamino)ethane,8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-dione,3-dodecyl-1-(2,2,6,6-tetramethyl-4-piperidyl)pyrrolidin-2,5-dione,3-dodecyl-1-(1,2,2,6,6-pentamethyl-4-piperidyl)pyrrolidine-2,5-dione, amixture of 4-hexadecyloxy- and4-stearyloxy-2,2,6,6-tetramethylpiperidine, a condensation product ofN,N′-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and4-cyclohexylamino-2,6-dichloro-1,3,5-triazine, a condensation product of1,2-bis(3-aminopropylamino)ethane and 2,4,6-trichloro-1,3,5-triazine aswell as 4-butylamino-2,2,6,6-tetramethylpiperidine (CAS Reg. No.[136504-96-6]); N-(2,2,6,6-tetramethyl-4-piperidyl)-n-dodecylsuccinimid,N-(1,2,2,6,6-pentamethyl-4-piperidyl)-n-dodecylsuccinimid,2-undecyl-7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxo-spiro[4,5]decane, areaction product of7,7,9,9-tetramethyl-2-cycloundecyl-1-oxa-3,8-diaza-4-oxospiro[4,5]decaneund epichlorohydrin,1,1-bis(1,2,2,6,6-pentamethyl-4-piperidyloxycarbonyl)-2-(4-methoxyphenyl)ethene,N,N′-bis-formyl-N,N′-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine,diester of 4-methoxy-methylene-malonic acid with1,2,2,6,6-pentamethyl-4-hydroxypiperidine,poly[methylpropyl-3-oxy-4-(2,2,6,6-tetramethyl-4-piperidyl)]siloxane,reaction product of maleic acid anhydride-α-olefin-copolymer with2,2,6,6-tetramethyl-4-aminopiperidine or1,2,2,6,6-pentamethyl-4-aminopiperidine.2.7. Oxamides, for example 4,4′-dioctyloxyoxanilide,2,2′-diethoxyoxanilide, 2,2′-dioctyloxy-5,5′-di-tert-butoxanilide,2,2′-didodecyloxy-5,5′-di-tert-butoxanilide, 2-ethoxy-2′-ethyloxanilide,N,N′-bis(3-dimethylaminopropyl)oxamide,2-ethoxy-5-tert-butyl-2′-ethoxanilide and its mixture with2-ethoxy-2′-ethyl-5,4′-di-tert-butoxanilide, mixtures of o- andp-methoxy-disubstituted oxanilides and mixtures of o- andp-ethoxy-disubstituted oxanilides.2.8. Tris-aryl-o-hydroxyphenyl-s-triazines, for example known commercialtris-aryl-o-hydroxyphenyl-s-triazines and triazines as disclosed in, WO96/28431 and U.S. Pat. Nos. 3,843,371; 4,619,956; 4,740,542; 5,096,489;5,106,891; 5,298,067; 5,300,414; 5,354,794; 5,461,151; 5,476,937;5,489,503; 5,543,518; 5,556,973; 5,597,854; 5,681,955; 5,726,309;5,736,597; 5,942,626; 5,959,008; 5,998,116; 6,013,704; 6,060,543;6,187,919; 6,242,598 and 6,255,483, for example4,6-bis-(2,4-dimethylphenyl)-2-(2-hydroxy-4-octyloxyphenyl)-s-triazine,Cyasorb® 1164, Cytec Corp,4,6-bis-(2,4-dimethylphenyl)-2-(2,4-dihydroxyphenyl)-s-triazine,2,4-bis(2,4-dihydroxyphenyl)-6-(4-chlorophenyl)-s-triazine,2,4-bis[2-hydroxy-4-(2-hydroxyethoxy)phenyl]-6-(4-chlorophenyl)-s-triazine,2,4-bis[2-hydroxy-4-(2-hydroxy-4-(2-hydroxyethoxy)phenyl]-6-(2,4-dimethylphenyl)-s-triazine,2,4-bis[2-hydroxy-4-(2-hydroxyethoxy)phenyl]-6-(4-bromophenyl)-s-triazine,2,4-bis[2-hydroxy-4-(2-acetoxyethoxy)phenyl]-6-(4-chlorophenyl)-s-triazine,2,4-bis(2,4-dihydroxyphenyl)-6-(2,4-dimethylphenyl)-s-triazine,2,4-bis(4-biphenylyl)-6-(2-hydroxy-4-octyloxycarbonylethylideneoxyphenyl)-s-trazine,2-phenyl-4-[2-hydroxy-4-(3-sec-butyloxy-2-hydroxypropyloxy)phenyl]-6-[2-hydroxy-4-(3-sec-amyloxy-2-hydroxypropyloxy)phenyl]-s-triazine,2,4-bis(2,4-dimethylphenyl)-6-[2-hydroxy-4-(3-benzyloxy-2-hydroxypropyloxy)phenyl]-s-triazine,2,4-bis(2-hydroxy-4-n-butyloxyphenyl)-6-(2,4-di-n-butyloxyphenyl)-s-triazine,2,4-bis(2,4-dimethylphenyl)-6-[2-hydroxy-4-(3-nonyloxy*-2-hydroxypropyloxy)-5-α-cumylphenyl]-s-triazine(* denotes a mixture of octyloxy, nonyloxy and decyloxy groups),methylenebis-{2,4-bis(2,4-dimethylphenyl)-6-[2-hydroxy-4-(3-butyloxy-2-hydroxypropoxy)phenyl]-s-triazine},methylene bridged dimer mixture bridged in the 3:5′, 5:5′ and 3:3′positions in a 5:4:1 ratio,2,4,6-tris(2-hydroxy-4-isooctyloxycarbonylisopropylideneoxyphenyl)-s-triazine,2,4-bis(2,4-dimethylphenyl)-6-(2-hydroxy-4-hexyloxy-5-α-cumylphenyl)-s-triazine,2-(2,4,6-trimethylphenyl)-4,6-bis[2-hydroxy-4-(3-butyloxy-2-hydroxypropyloxy)phenyl]-s-triazine,2,4,6-tris[2-hydroxy-4-(3-sec-butyloxy-2-hydroxypropyloxy)phenyl]-s-triazine,mixture of4,6-bis-(2,4-dimethylphenyl)-2-(2-hydroxy-4-(3-dodecyloxy-2-hydroxypropoxy)-phenyl)-s-triazineand4,6-bis-(2,4-dimethylphenyl)-2-(2-hydroxy-4-(3-tridecyloxy-2-hydroxypropoxy)-phenyl)-s-triazine,Tinuvin® 400, Ciba Specialty Chemicals Corp.,4,6-bis-(2,4-dimethylphenyl)-2-(2-hydroxy-4-(3-(2-ethylhexyloxy)-2-hydroxypropoxy)-phenyl)-s-triazineand 4,6-diphenyl-2-(4-hexyloxy-2-hydroxyphenyl)-s-triazine.3. Metal deactivators, for example N,N′-diphenyloxamide,N-salicylal-N′-salicyloyl hydrazine, N,N′-bis(salicyloyl)hydrazine,N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazine,3-salicyloylamino-1,2,4-triazole, bis(benzylidene)oxalyl dihydrazide,oxanilide, isophthaloyl dihydrazide, sebacoyl bisphenylhydrazide,N,N′-diacetyladipoyl dihydrazide, N,N′-bis(salicyloyl)oxalyldihydrazide, N,N′-bis(salicyloyl)thiopropionyl dihydrazide.4. Phosphites and phosphonites, for example triphenyl phosphite,diphenyl alkyl phosphites, phenyl dialkyl phosphites,tris(nonylphenyl)phosphite, trilauryl phosphite, trioctadecyl phosphite,distearyl pentaerythritol diphosphite,tris(2,4-di-tert-butylphenyl)phosphite, diisodecyl pentaerythritoldiphosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite,bis(2,6-di-tert-butyl-4-methylphenyl)-pentaerythritol diphosphite,diisodecyloxypentaerythritol diphosphite,bis(2,4-di-tert-butyl-6-methylphenyl)pentaerythritol diphosphite,bis(2,4,6-tris(tert-butylphenyl)pentaerythritol diphosphite, tristearylsorbitol triphosphite, tetrakis(2,4-di-tert-butylphenyl)4,4′-biphenylene diphosphonite,6-isooctyloxy-2,4,8,10-tetra-tert-butyl-12H-dibenz[d,g]-1,3,2-dioxaphosphocin,bis(2,4-di-tert-butyl-6-methylphenyl)methyl phosphite,bis(2,4-di-tert-butyl-6-methylphenyl)ethyl phosphite,6-fluoro-2,4,8,10-tetra-tert-butyl-12-methyl-dibenz[d,g]-1,3,2-dioxaphosphocin,2,2′,2″-nitrilo[triethyltris(3,3′,5,5′-tetra-tert-butyl-1,1′-biphenyl-2,2′-diyl)phosphite],2-ethylhexyl(3,3′,5,5′-tetra-tert-butyl-1,1′-biphenyl-2,2′-diyl)phosphite,5-butyl-5-ethyl-2-(2,4,6-tri-tert-butylphenoxy)-1,3,2-dioxaphosphirane.

Specific examples are the following phosphites:

Tris(2,4-di-tert-butylphenyl)phosphite (Irgafos®168, Ciba-Geigy),tris(nonylphenyl)phosphite,

5. Hydroxylamines, for example, N,N-dibenzylhydroxylamine,N,N-diethylhydroxylamine, N,N-dioctylhydroxylamine,N,N-dilaurylhydroxylamine, N,N-ditetradecylhydroxylamine,N,N-dihexadecylhydroxylamine, N,N-dioctadecylhydroxylamine,N-hexadecyl-N-octadecylhydroxylamine,N-heptadecyl-N-octadecylhydroxylamine, N,N-dialkylhydroxylamine derivedfrom hydrogenated tallow amine.6. Nitrones, for example, N-benzyl-alpha-phenyl-nitrone,N-ethyl-alpha-methyl-nitrone, N-octyl-alpha-heptyl-nitrone,N-lauryl-alpha-undecyl-nitrone, N-tetradecyl-alpha-tridcyl-nitrone,N-hexadecyl-alpha-pentadecyl-nitrone,N-octadecyl-alpha-heptadecyl-nitrone,N-hexadecyl-alpha-heptadecyl-nitrone,N-ocatadecyl-alpha-pentadecyl-nitrone,N-heptadecyl-alpha-heptadecyl-nitrone,N-octadecyl-alpha-hexadecyl-nitrone, nitrone derived fromN,N-dialkylhydroxylamine derived from hydrogenated tallow amine.7. Thiosyneraists, for example, dilauryl thiodipropionate or distearylthiodipropionate.8. Peroxide scavengers, for example esters of β-thiodipropionic acid,for example the lauryl, stearyl, myristyl or tridecyl esters,mercaptobenzimidazole or the zinc salt of 2-mercaptobenzimidazole, zincdibutyldithiocarbamate, dioctadecyl disulfide, pentaerythritoltetrakis(β-dodecylmercapto)propionate.9. Polyamide stabilizers, for example, copper salts in combination withiodides and/or phosphorus compounds and salts of divalent manganese.10. Basic co-stabilizers, for example, melamine, polyvinylpyrrolidone,dicyandiamide, triallyl cyanurate, urea derivatives, hydrazinederivatives, amines, polyamides, polyurethanes, alkali metal salts andalkaline earth metal salts of higher fatty acids for example calciumstearate, zinc stearate, magnesium behenate, magnesium stearate, sodiumricinoleate and potassium palmitate, antimony pyrocatecholate or zinkpyrocatecholate.11. Nucleating agents, for example, inorganic substances such as talcum,metal oxides such as titanium dioxide or magnesium oxide, phosphates,carbonates or sulfates of, for example, alkaline earth metals; organiccompounds such as mono- or polycarboxylic acids and the salts thereof,e.g. 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid, sodiumsuccinate or sodium benzoate; polymeric compounds such as ioniccopolymers (ionomers). Specific examples are1,3:2,4-bis(3′,4′-dimethylbenzylidene)sorbitol,1,3:2,4-di(paramethyldibenzylidene)sorbitol, und1,3:2,4-di(benzylidene)sorbitol.12. Fillers and reinforcing agents, for example, calcium carbonate,silicates, glass fibres, glass bulbs, asbestos, talc, kaolin, mica,barium sulfate, metal oxides and hydroxides, carbon black, graphite,wood flour and flours or fibers of other natural products, syntheticfibers.13. Other additives, for example, plasticisers, lubricants, emulsifiers,pigments, rheology additives, catalysts, flow-control agents, opticalbrighteners, flameproofing agents, antistatic agents and blowing agents.14. Benzofuranones and indolinones, for example those disclosed in U.S.Pat. No. 4,325,863; U.S. Pat. No. 4,338,244; U.S. Pat. No. 5,175,312;U.S. Pat. No. 5,216,052; U.S. Pat. No. 5,252,643; DE-A-4316611;DE-A4316622; DE-A4316876; EP-A-0589839 or EP-A-0591102 or3-[4-(2-acetoxyethoxy)phenyl]-5,7-di-tert-butyl-benzofuran-2-one,5,7-di-tert-butyl-3-[4-(2-stearoyloxyethoxy)phenyl]benzofuran-2-one,3,3′-bis[5,7-di-tert-butyl-3-(4-[2-hydroxyethoxy]phenyl)benzofuran-2-one],5,7-di-tert-butyl-3-(4-ethoxyphenyl)benzofuran-2-one,3-(4-acetoxy-3,5-dimethylphenyl)-5,7-di-tert-butyl-benzofuran-2-one,3-(3,5-dimethyl-4-pivaloyloxyphenyl)-5,7-di-tert-butyl-benzofuran-2-one,3-(3,4-dimethylphenyl)-5,7-di-tert-butyl-benzofuran-2-one,3-(2,3-dimethylphenyl)-5,7-di-tert-butyl-benzofuran-2-one.15. Amine oxides, for example amine oxide derivatives as disclosed inU.S. Pat. Nos. 5,844,029 and 5,880,191, didecyl methyl amine oxide,tridecyl amine oxide, tridodecyl amine oxide and trihexadecyl amineoxide. U.S. Pat. Nos. 5,844,029 and 5,880,191 disclose the use ofsaturated hydrocarbon amine oxides towards the stabilization ofthermoplastic resins. It is disclosed that the thermoplasticcompositions may further contain a stabilizer or mixture of stabilizersselected from phenolic antioxidants, hindered amine light stabilizers,ultraviolet light absorbers, organic phosphorus compounds, alkalinemetal salts of fatty acids and thiosynergists. The co-use of amineoxides with other stabilizers towards stabilizing polyolefins is notexemplified.

Specific examples of additives are phenolic antioxidants (item 1 of thelist), further sterically hindered amines (item 2.6 of the list), lightstabilizers of the benzotriazole and/or ohydroxyphenyltriazine class(items 2.1 and 2.8 of the list), phosphites and phosphonites (item 4 ofthe list) and peroxide-destroying compounds (item 5.) of the list.

Additional specific examples of additives (stabilizers) which arebenzofuran-2-ones, such as described, for example, in U.S. Pat. No.4,325,863, U.S. Pat. No. 4,338,244 or U.S. Pat. No. 5,175,312.

The instant composition can additionally contain another UV absorberselected from the group consisting of the s-triazines, the oxanilides,the hydroxybenzophenones, benzoates and the α-cyanoacrylates.Particularly, the instant composition may additionally contain aneffective stabilizing amount of at least one other2-hydroxyphenyl-2H-benzotriazole; another tris-aryl-s-triazine; orhindered amine or mixtures thereof. For example, additional componentsare selected from pigments, dyes, plasticizers, antioxidants,thixotropic agents, levelling assistants, basic costabilizers, furtherlight stabilizers like UV absorbers and/or sterically hindered amines,metal passivators, metal oxides, organophosphorus compounds,hydroxylamines, and mixtures thereof, especially pigments, phenolicantioxidants, calcium stearate, zinc stearate, UV absorbers of the2-(2′-hydroxyphenyl)benzotriazole and 2-(2-hydroxyphenyl)-1,3,5-triazineclasses, and sterically hindered amines.

The additives of the invention and optional further components may beadded to the polymer material individually or mixed with one another. Ifdesired, the individual components can be mixed with one another beforeincorporation into the polymer for example by dry blending, compactionor in the melt. Subject of the invention therefore is also a flameretardant additive combination comprising

-   -   (i) at least one sterically hindered amine stabilizer and    -   (ii) at least one conventional flame retardant selected from the        group consisting of the organohalogen, phosphorus containing,        isocyanurate and melamine based flame retardants and    -   (iii) at least one acid scavenger.

Conveniently, the additives of above components (i), (ii) and (iii) andpossibly further additives as described above may be dry blended andthen extruded, for instance in a twin screw extruder at 180–220° C.,with or without nitrogen atmosphere. The material thus obtained may befurther processed according to known methods. The surface of thearticles formed do not show any loss of gloss or any kind of roughness.

Further, the instant invention pertains to a process for imparting lightstability and flame retardancy to an organic polymeric substrate, whichprocess comprises adding to said polymeric substrate an effective flameretarding amount of a synergistic mixture of

-   -   (i) at least one sterically hindered amine stabilizer,    -   (ii) at least one conventional flame retardant selected from the        group consisting of the organohalogen, phosphorus containing,        isocyanurate and melamine based flame retardants and    -   (iii) at least one acid scavenger.

The incorporation of the additives of the invention and optional furthercomponents into the polymer is carried out by known methods such as dryblending in the form of a powder, or wet mixing in the form ofsolutions, dispersions or suspensions for example in an inert solvent,water or oil. The additives of the invention and optional furtheradditives may be incorporated, for example, before or after molding oralso by applying the dissolved or dispersed additve or additive mixtureto the polymer material, with or without subsequent evaporation of thesolvent or the suspension/dispersion agent. They may be added directlyinto the processing apparatus (e.g. extruders, internal mixers, etc),e.g. as a dry mixture or powder or as solution or dispersion orsuspension or melt.

The incorporation can be carried out in any heatable container equippedwith a stirrer, e.g. in a closed apparatus such as a kneader, mixer orstirred vessel. The incorporation is for example carried out in anextruder or in a kneader. It is immaterial whether processing takesplace in an inert atmosphere or in the presence of oxygen.

The addition of the additive or additive blend to the polymer can becarried out in all customary mixing machines in which the polymer ismelted and mixed with the additives. Suitable machines are known tothose skilled in the art. They are predominantly mixers, kneaders andextruders.

The process is for instance carried out in an extruder by introducingthe additive during processing.

Specific examples of suitable processing machines are single-screwextruders, contrarotating and corotating twin-screw extruders,planetary-gear extruders, ring extruders or cokneaders. It is alsopossible to use processing machines provided with at least one gasremoval compartment to which a vacuum can be applied.

Suitable extruders and kneaders are described, for example, in Handbuchder Kunststoffextrusion, Vol. 1 Grundlagen, Editors F. Hensen, W.Knappe, H. Potente, 1989, pp. 3–7, ISBN:3-446-14339-4 (Vol. 2Extrusionsanlagen 1986, ISBN 3-446-14329-7).

For example, the screw length is 1–60 screw diameters, for example 3548screw diameters. The rotational speed of the screw is for instance10–600 rotations per minute (rpm), for example 25–300 rpm.

The maximum throughput is dependent on the screw diameter, therotational speed and the driving force. The process of the presentinvention can also be carried out at a level lower than maximumthroughput by varying the parameters mentioned or employing weighingmachines delivering dosage amounts.

If a plurality of components are added, these can be premixed or addedindividually.

The additives of the invention and optional further additives can alsobe sprayed onto the polymer material. They are able to dilute otheradditives (for example the conventional additives indicated above) ortheir melts so that they can be sprayed also together with theseadditives onto the material. Addition by spraying during thedeactivation of the polymerization catalysts is particularlyadvantageous; in this case, the steam evolved may be used fordeactivation of the catalyst. In the case of spherically polymerizedpolyolefins it may, for example, be advantageous to apply the additivesof the invention, optionally together with other additives, by spraying.

The additives of the invention and optional further additives can alsobe added to the polymer in the form of a masterbatch (“concentrate”)which contains the components in a concentration of, for example, about1% to about 40%, for example about 2% to about 20% by weightincorporated in a polymer. The polymer must not be necessarily ofidentical structure than the polymer where the additives are addedfinally. In such operations, the polymer can be used in the form ofpowder, granules, solutions, suspensions or in the form of latices.

Incorporation can take place prior to or during the shaping operation.The materials containing the additives of the invention described hereinare for example used for the production of molded articles, for examplerotomolded articles, injection molded articles, profiles and the like.Thus, a molded polymer article made flame retardant by the incorporationof

-   -   (i) at least one sterically hindered amine stabilizer and    -   (ii) at least one conventional flame retardant selected from the        group consisting of the organohalogen, phosphorus containing,        isocyanurate and melamine based flame retardants and    -   (iii) at least one acid scavenger        is another object of the invention.

It is also contemplated that PTFE, polytetrafluoroethylene (for exampleTeflon® 6C; E. I. Du Pont), may be advantageously added to the presentcompositions as an additional flame retardant, as disclosed in U.S.application 60/312,517, filed Aug. 15, 2001.

It has further unexpectedly been observed that polymer molded articles,which normally comprise large amounts of flame-retardant filler in orderto maintain flame retardant properties, may be stabilized against light,heat and oxygen and made flame retardant, by the incorporation thereinof present components (i), (ii) and (iii), and the amount offlame-retardant filler necessary is greatly reduced or even totallyeliminated. The polymer molded articles are for example polyolefinmolded articles, for example thin-section articles. The flame-retardantfiller is typically magnesium hydroxide.

The thin-section polyolefin molded articles advantageously comprisepresent components (i), (ii) and (iii). The polyolefin molded articlesof this invention, with reduced levels of flame-retardant filler or noflame-retardant filler, maintain flame retardancy and have improvedphysical properties.

The polyolefin molded articles of this invention may be used for exampleas roofing membranes, siding, window profiles and moldings. Such moldedarticles are for example about 5 mil to about 100 mil thick, for exampleabout 20 mil to about 100 mil thick, for instance about 10 mil to about80 mil, for example about 40 mil to about 100 mil thick. The polyolefinis in particular thermoplastic polyolefin (TPO). The molded articles ofthis invention exhibit better physical properties than the state of theart formulations, as exhibited by mechanical properties such as tensilestrength, elongation resistance and crack resistance.

The effective flame retarding amount of component (B) is that needed toshow flame retarding efficacy as measured by one of the standard methodsused to assess flame retardancy. These include the NFPA 701 StandardMethods of Fire Tests for Flame-Resistant Textiles and Films, 1989 and1996 editions; the UL 94 Test for Flammability of Plastic Materials forParts in Devices and Appliances, 5th Edition, Oct. 29, 1996; LimitingOxygen Index (LOI), ASTM D-2863; and Cone Calorimetry, ASTM E-1354.Ratings according to the UL 94 V test are as compiled in the followingtable:

Afterflame Burning Burn to Rating time drips Clamp V-0 <10 s no no V-1<30 s no no V-2 <30 s yes no Fail <30 s yes Fail >30 s no

Coadditives found particularly useful for use with the instantcombination of components (i), (ii) and (iii) in flame retardantcompositions are as follows:

UV absorbers:

2-(2-hydroxy-3,5-di-α-cumylphenyl)-2H-benzotriazole, (TINUVIN® 234, CibaSpecialty Chemicals Corp.);

2-(2-hydroxy-5-methylphenyl)-2H-benzotriazole, (TINUVIN® P, CibaSpecialty Chemicals Corp.);

5-chloro-2-(2-hydroxy-3,5-di-tert-butylphenyl)-2H-benzotriazole,(TINUVIN® 327, Ciba Specialty Chemicals Corp.);

2-(2-hydroxy-3,5-di-tert-amylphenyl)-2H-benzotriazole, (TINUVIN® 328,Ciba Specialty Chemicals Corp.);

2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole, (TINUVIN®928, Ciba Specialty Chemicals Corp.);

2,4-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate, (TINUVIN®120, Ciba Specialty Chemicals Corp.);

2-hydroxy-4-n-octyloxybenzophenone, (CHIMASSORB® 81, Ciba SpecialtyChemicals Corp.);

2,4-bis(2,4-dimethyphenyl)-6-(2-hydroxy-4-octyloxyphenyl)-s-triazine,(CYASORB® 1164, Cytec).

The following examples are meant for illustrative purposes only and arenot to be construed to limit the scope of this invention in any mannerwhatsoever. Where given, room temperature depicts a temperature in therange 20–25° C. Percentages are by weight of the polymer substrateunless otherwise indicated.

Abbreviations:

Abbreviations: v parts by volume w parts by weight ¹Hnmr nuclearmagnetic resonance (NMR) of ¹H m/z mass spectrometry (atomic units) amumolecular weight in g/mol (= atomic units) PP polypropylene PEpolyethylene PE-LD low density polyethylene (LDPE)Test Methods

NFPA 701 Standard Methods of Fire Tests for Flame-Resistant Textiles andFilms, 1989 and 1996 editions;

UL 94 Test for Flammability of Plastic Materials for Parts in Devicesand Appliances, 5th Edition, Oct. 29, 1996;

Limiting Oxygen Index (LOI), ASTM D-2863;

Cone Calorimetry, ASTM E-1 or ASTM E 1354;

ASTM D 2633–82, burn test.

Test Compounds

Hindered amines of present component (i):

NOR1 1-cyclohexyloxy-2,2,6,6-tetramethyl-4-octadecylaminopiperidine;

NOR2 bis(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl)sebacate;

NOR32,4-bis[(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)butylamino]-6-(2-hydroxyethylamino-s-triazine;

NOR42,4-bis[(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)butylamino]-6-chloro-s-triazine;

NOR51-(2-hydroxy-2-methylpropoxy)-4-hydroxy-2,2,6,6-tetramethylpiperidine;

NOR6 1-(2-hydroxy-2-methylpropoxy)-4-oxo-2,2,6,6-tetramethylpiperidine;

NOR71-(2-hydroxy-2-methylpropoxy)-4-octadecanoyloxy-2,2,6,6-tetramethylpiperidine;

NOR8bis(1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl)sebacate;

NOR9bis(1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl)adipate;

NOR102,4-bis{N-[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl]-N-butylamino}-6-(2-hydroxyethylamino)-s-triazine;

NOR11 the reaction product of2,4-bis[(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)butylamino]-6-chloro-s-triazinewith N,N′-bis(3-aminopropyl)ethylenediamine) [CAS Reg. No. 191680-81-6];

NOR11 is represented as a mixture of compounds with main component ofthe formulaR₁NH—CH₂CH₂CH₂NR₂CH₂CH₂NR₃CH₂CH₂CH₂NHR₄

-   -   wherein 3 of R₁, R₂, R₃ and R₄ are residues of formula

and 1 of R₁, R₂, R₃ and R₄ is hydrogen (NOR11 is a high molecolar weightcompound disclosed in example 3 of U.S. Pat. No. 5,844,026); and

NOR12 the compound of formula

in which n is from 1 to 15; and

NOR13 bis(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)adipate.

Conventional flame retardants of component (ii):

-   DBDPO is decabromodiphenyl oxide,-   FR1 tris[3-bromo-2,2-bis(bromomethyl)propyl] phosphate, (PB 370®,    FMC Corp.),-   FR2 ammonium polyphosphate (APP),-   FR3 bis(2,3-dibromopropyl)ether of tetrabromobisphenol A (PE68),-   FR4 ammonium polyphosphate/synergist blend, HOSTAFLAM® AP750,-   FR5 decabromodiphenyl oxide (DBDPO; obtained from Dead Sea Bromine),-   FR6 ethylene bis-(tetrabromophthalimide), (SAYTEX® BT-93),-   FR7 melamine phosphate, MELAPUR® P 46,-   FR8 ammonium polyphosphate, EXOLIT® AP752,-   FR9 tris-(2,3-dibromopropyl)-isocyanurate,-   FR10 hexabromocyclododecane,-   FR11 melamine cyanurate, MELAPUR® MC,-   FR12 melamine borate,-   FR13 melamine polyphosphate MELAPUR® 200 and-   FR14 melamine pyrophosphate.

Compounds NOR2, NOR7, NOR11, NOR12 are commercial stabilizers availablefrom Ciba Specialty Chemicals. MELAPUR products are available from DSM.

EXAMPLE 1 Flame Retardant Polypropylene

Additives are dry mixed and extruded with polypropylene homopolymerresin with a twin screw (27 mm) extruder at 200° C. under nitrogen.Weight percents are based on the polymer. From the pellets, 1.6 mmplaques are prepared by injection molding. The plaques are testedaccording to UL 94 protocol after 48 hours conditioning at 25° C. and50% humidity. Plaques containing 1% by weight NOR11, the reactionproduct of2,4-bis[(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)butylamino]-6-chloro-s-triazinewith N,N′-bis(3-aminopropyl)ethylenediamine), and 14% by weighttris[3-bromo-2,2-bis(bromomethyl)propyl]phosphate and 0.6% by weight ofa present acid scavenger achieve a V-0 rating. The plaques also exhibitexcellent color, odor and stability.

EXAMPLE 2

Sample preparation: Polymer powder and stabilizers are pre-mixed(Henschel mixer, 800 rpm, room temperature), pigment powder and flameretardant are added as concentrate in PP and homogenized in a drummixer. Further homogenization and granulation is achieved by extrusion(Collin® twin screw extruder, max 200° C., 100 rpm). Subsequently, themixture is processed into a flat film by means of a single screwextruder (max 200° C., 70 rpm) equipped with a corresponding nozzle(sample dimension 2 mm thickness, 10 cm width).

Weathering: Punched samples are exposed to accelerated weathering(Atlas® WOM Ci 65, 0.35W/m² (at 340 nm), 102 min dry, 18 min waterspray, 63° C. black panel temperature. The effect of weathering on thesurface is assessed in the following manner:

-   Visual inspection of chalking (chalking indicates decomposition on    the surface).-   Gloss: Minolta; degradation of surface reduces the reflection of    polarized light (60° gloss as defined in DIN 67530).-   ΔE: Color change (according to DIN 6174).

Formulation:

-   84 parts by weight of polypropylene-ethylene copolymer (Novolen® PPG    1022),-   15 parts by weight of a PE-based flame retardant masterbatch    containing 51% by weight of FR1,-   1 part by weight of TiO₂ and-   0.2 parts by weight of blue pigment (Cromophtal blue 4GNP)-   0.4 parts of an NOR selected from NOR1–NOR12-   0.1 part present acid scavenger.

Samples containing the combination of flame retardant and stericallyhindered amines of the present invention and a present acid scavengershow no chalking, excellent gloss and distinctly low color change.

EXAMPLE 3

Samples are prepared and subjected to accelerated weathering asdescribed in Example 2.

Formulation:

-   89 parts by weight of polypropylene-ethylene copolymer (Novolen® PPG    1022),-   10 parts by weight of a PE based flame retardant masterbatch    containing 30% by weight of FR1,-   1 part by weight of TiO₂ and-   0.2 parts by weight of blue pigment (Cromophtal blue 4GNP)-   0.4 parts of an NOR stabilizer selected from NOR1–NOR12-   0.1 part present acid scavenger.

Excellent results are achieved.

EXAMPLE 4

Samples are prepared and subjected to accelerated weathering asdescribed in Example 2.

Formulation:

-   94 parts by weight of polypropylene-ethylene copolymer (Novolen®D    PPG 1022),-   4 parts by weight of FR1,-   0.2 parts by weight of blue pigment (Cromophtal blue 4GNP)-   0.4 parts of an NOR selected from NOR1–NOR12-   0.5 part present acid scavenger.

Excellent results are achieved.

EXAMPLE 5

Samples are prepared and subjected to accelerated weathering asdescribed in Example 2.

Formulation:

-   87.5 parts by weight of polypropylene-ethylene copolymer (Novolen®    PPG 1022),-   8 parts by weight of a PE based flame retardant masterbatch    containing 40% by weight of FR1-   1 part by weight of TiO₂ and-   0.2 parts by weight of blue pigment (Cromophtal blue 4GNP)-   0.4 parts of an NOR selected from NOR1–NOR12 and-   0.5 part present acid scavenger.

Excellent results are achieved.

EXAMPLE 6

Examples 2–5 are repeated, replacing FR1 with a conventional flameretardant selected from FR2–FR14. Excellent results are achieved.

EXAMPLE 7 TPO Roofing Membranes

This example illustrates that by employing the present stabilizing andflame retarding system of components (i), (ii) and (iii), thatflame-retardant filler (typically magnesium hydroxide) may be replacedin polyolefin molded articles. The polyolefin molded articles of thisinvention maintain flame retardancy and have improved physicalproperties.

The polyolefin molded articles of this invention may be used for exampleas roofing membranes, siding, window profiles and moldings. Such moldedarticles are for example about 5 mil to about 100 mil thick. Thepolyolefin is in particular thermoplastic polyolefin (TPO). The moldedarticles of this invention exhibit better physical properties than thestate of the art formulations, as exhibited by mechanical propertiessuch as tensile strength, elongation resistance and crack resistance.

A typical state of the art formulation for such applications is forexample:

parts Polypropylene copolymer 100 TiO₂ or carbon black 3 CaCo₃ 5Magnesium hydroxide 35 UV stabilizer 1 Lubricant or other 1

The state of the art formulation requires that either TiO₂ or carbonblack are present and that magnesium hydroxide is present.

In the formulations of the present invention, magnesium hydroxide isreplaced with a sterically hindered amine compound selected fromNOR1–NOR12, and a traditional flame retardant selected from FR1–FR14.

The formulation of the present invention is for example:

parts Polypropylene copolymer 100 TiO₂ or carbon black 3 CaCO₃ 0–5Magnesium hydroxide 0 NOR7 1.0 FR1 4 UV stabilizer 1 Present acidscavenger 1

NOR7 may be replaced for example with another hindered amine selectedfrom NOR1–NOR12. FR1 may be replaced with a flame retardant selectedfrom FR2–FR14. The molded articles of the present invention exhibitexcellent flame retardancy and improved physical properties as comparedto state of the art molded articles.

EXAMPLE 8

Molding grade polypropylene (Profax® 6501; Basell) is dry blended withtest additives selected from components (i), (ii) and (iii) and thenmelt compounded in a twin screw extruder at 220° C. Base stabilizationis 500 ppm N,N-di(alkyl)hydroxylamine produced by the direct oxidationof N,N-di(hydrogenated tallow)amine (Irgastab® FS-042) and 500 ppmcalcium stearate. Plaques (125 mil) are prepared by injection moldingfrom the formulations using a Boy Injection Molder at 475° F. (246° C.).The specimens are tested for flame retardancy according to the UL-94vertical burn test specifications.

Plaques containing an amine selected from NOR1–NOR12, a conventionalflame retardant selected from FR1–FR14 and an acid scavenger exhibitexcellent flame retardant properties.

EXAMPLE 9

Polyethylene fibers are prepared from fiber grade polyethylene by dryblending with test additives and melt compounding at 400° F. Fibers areextruded from this formulation using a Hills laboratory scale fiberextruder. Socks are knitted from the fibers and are tested for flameretardancy according to NFPA 701 vertical burn method. Polyethylenefibers contain 0.5%, 1% or 2% by weight, total, of an additive selectedfrom NOR1–NOR12, and further with 10% by weight of a classic flameretardant selected from FR1–FR14 and an acid scavenger (hycite). Theseformulated fibers are tested for flame retardancy according to NFPA 701.

The fibers containing additive combinations of present components (i),(ii) and (iii) exhibit excellent flame retardancy.

EXAMPLE 10

Molding grade polypropylene (Profax® 6501; Basell) is dry blended withan amine selected from NOR1–NOR12, 10% of FR1 and 1% present acidscavenger, and then melt compounded in a twin screw extruder at 200° C.under nitrogen. Base stabilization is 500 ppm N,N-di(alkyl)hydroxylamineproduced by the direct oxidation of N,N-di(hydrogenated tallow)amine(Irgastab®FS-042) and 500 ppm calcium stearate. Plaques (125 mil) areprepared by injection molding from the formulations using a BoyInjection Molder at 475° F. (246° C.). The specimens are tested forflame retardancy according to the UL-94 vertical burn testspecifications.

The plaques are tested for flame retardancy by the UL 94V thick sectiontest. The ratings achievable are V-0 (best rating), V-1, and V-2. Theplaques containing the three-component additive system of the presentinvention exhibit excellent flame retardancy.

EXAMPLE 11

Foam grade polyethylene is dry blended with test additives and then meltcompounded into pellets. The pelletized fully formulated resin is thenblown into foam.

The polyethylene foam prepared contains an instant additive selectedfrom NOR1–NOR12, a flame retardant FR1–FR14 and a present acidscavenger. The formulated foam is tested for flame retardancy accordingto the UL-94 burn test method.

The foam containing an additive combination of present components (i),(ii) and (iii) exhibits excellent flame retardancy.

EXAMPLE 12

Wire & cable grade polyethylene is dry blended with test additives andthen melt compounded into pellets. The pelletized fully formulated resinis then extruded onto wire.

Test specimens are tested for flame retardancy using the ASTM D 2633–82burn test conditions. The formulations containing a compound selectedfrom NOR1–NOR12, a classic flame retardant selected from FR1–FR14 and apresent acid scavenger, exhibits excellent flame retardancy.

EXAMPLE 13

Fiber grade polyethylene is dry-blended with test additives. Non-wovenfabrics are produced from the polymer blend formulations by aspun-bonded or melt-blown process.

The non-woven fabrics made thereby are tested for flame retardancyaccording to the NFPA 701 vertical burn test specifications. The fabricscontaining a compound selected from NOR1–NOR12, a selected conventionalflame retardant and a present acid scavenger exhibit excellent flameretardancy.

EXAMPLE 14

Fiber grade polypropylene is dry-blended with test additives. Non-wovenfabrics are produced from the polymer blend formulations by aspun-bonded or melt-blown process.

The non-woven fabrics made thereby are tested for flame retardancyaccording to the NFPA 701 vertical burn test specifications. The fabricscontaining an additive selected from NOR1–NOR12, selected conventionalflame retardants and a present acid scavenger exhibit excellent flameretardancy.

EXAMPLE 15

Molding grade polystyrene is dry-blended with test additives and thenmelt compounded. Specimens are injection molded from these testformulations.

The specimens are tested for flame retardancy according to the UL-94burn test specifications. The molded specimens containing a presentcompound selected from NOR1–NOR12, selected conventional flameretardants and a present acid scavenger exhibit excellent flameretardancy.

EXAMPLE 16

Foam grade polystyrene is dry-blended with test additives and then meltcompounded. Foam polystyrene specimens are prepared from these testformulations.

The specimens are tested for flame retardancy according to the UL-94burn test specifications. The foam specimens containing a presentcompound selected from NOR1–NOR12, conventional flame retardants and apresent acid scavenger exhibit excellent flame retardancy.

EXAMPLE 17

Molding grade ABS is dry blended with test additives and then meltcompounded at 425° F. (218° C.). Specimens 125 mil (⅛″) thick are theninjection molded from this formulation using a Boy Injection Molder at450° F. (232° C.). The specimens are tested for flame retardancyaccording to the UL-94 vertical burn test specifications.

The specimens containing a present compound selected from NOR1–NOR12,conventional flame retardants and a present acid scavenger exhibitexcellent flame retardancy.

EXAMPLE 18

Fiber grade polypropylene is dry blended with test additives and thenmelt compounded at 234° C. (450° F.) into pellets. The pelletized fullyformulated resin is then spun at 246° C. (475° F.) into fiber using aHills laboratory model fiber extruder. The spun tow of 41 filaments isstretched at a ratio of 1:3.2 to give a final denier of 615/41.

Socks are knitted from the stabilized polypropylene fiber on aLawson-Hemphill Analysis Knitter and tested under NFPA 701 vertical burnprocedure. The time in seconds for the knitted sock to extinguish afterthe insult flame is removed is reported as “After Flame”. Both themaximum time for any one replicate and the total time for ten replicatesare measured. Efficacy as a flame retardant is demonstrated when lowAfter Flame times are observed relative to a blank sample containing noflame retardant.

The specimens containing a present compound selected from NOR1–NOR12,conventional flame retardants and a present acid scavenger exhibitexcellent flame retardancy.

EXAMPLE 19

Film grade polyethylene is dry blended with test additives and then meltcompounded into pellets. The pelletized fully formulated resin is thenblown at 205° C. using a MPM Superior Blown film extruder.

The films are tested for flame retardancy under NFPA 701 testconditions. The specimens containing a present compound selected fromNOR1–NOR12, conventional flame retardants and a present acid scavengerexhibit excellent flame retardancy.

Film grade polypropylene is handled in a similar fashion andpolypropylene films containing the present additive combinations alsoshow excellent flame retardancy.

EXAMPLE 20

Molded test specimens are prepared by injection molding thermoplasticolefin (TPO) pellets containing a present additive combination. The TPOformulations may also contain a pigment, a phosphite, a phenolicantioxidant or hydroxylamine, a metal stearate, a UV absorber or ahindered amine stabilizer or a mixture of hindered amine and UVabsorber.

Pigmented TPO formulation composed of polypropylene blended with arubber modifier where the rubber modifier is an in-situ reactedcopolymer or blended product containing copolymers of propylene andethylene with or without a ternary component such as ethylidenenorbornene are stabilized with a base stabilization system consisting ofan N,N-dialkylhydroxylamine or a mixture of hindered phenolicantioxidant and an organophosphorus compound.

The TPO plaques are tested for flame retardancy using the UL-94 VerticalBurn conditions. A minimum of three replicates are tested. Efficacy as aflame retardant is measured relative to a blank sample containing noflame retardant.

The specimens containing a present compound selected from NOR1–NOR12,conventional flame retardants and a present acid scavenger exhibitexcellent flame retardancy.

EXAMPLE 21

Film grade ethylene/vinyl acetate (EVA) copolymers containing 20 weightpercent or less of vinyl acetate are dry blended with test additives andthen melt compounded into pellets. The pelletized fully formulated resinis then blown into a film at 205° C. using a MPM Superior Blown-filmextruder.

The films are tested for flame retardancy under NFPA 701 testconditions. The films containing a present compound selected fromNOR1–NOR12, conventional flame retardants and a present acid scavengerexhibit excellent flame retardancy.

Film grade low density polyethylene (LDPE) which contains some linearlow density polyethylene (LLDPE) and/or ethylene/vinyl acetate (EVA) aredry blended with test additives and blown into film as described abovefor EVA copolymer resin. The films are tested for flame retardancy underNFPA 701 test conditions and those containing a present compoundselected from NOR1–NOR12, conventional flame retardants and a presentacid scavenger exhibit excellent flame retardancy.

EXAMPLE 22

High impact polystyrene (HIPS) polymer (STYRON® 484C, Dow Chemical Co.)is compounded with test additives, pelletized and then injection orcompression molded into plaques. These plaques are tested for flameretardant efficacy using cone calorimetry, LOI or UL-94 test method.

The plaques containing an instant compound selected from NOR1–NOR12, aselect conventional flame retardant and a present acid scavenger exhibitexcellent flame retardancy. Flame retardant HIPS polymers findapplication in housings for business machines.

EXAMPLE 23

This Example shows the efficacy of the present compound combinations inPVC formulations. Such formulations are useful in flexible or rigid PVCand in wire and cable applications.

Typical formulations are seen below:

Component parts parts parts parts PVC resin 100 100 100 100 tinmercaptide 1.5 — 2.0 — tin carboxyate — 2.5 — 2.0 process aid 1.5 1.52.0 2.0 impact mod. 6.0 6.0 7.0 7.0 paraffin wax 1.0 0.3 1.0 1.0polyethyl wax 0.1 0.1 0.2 0.2 Ca stearate 1.0 — 0.8 — pigment 1.0 0.95.0 5.0

Fully formulated PVC containing a compound selected from NOR1–NOR12, aconventional flame retardant and a present acid scavenger is pelletizedand then injection molded into test plaques for examination of flameretardancy using the UL-94 or LOI test method.

The PVC plaques containing the instant compound combinations demonstrateexcellent flame retardancy.

EXAMPLE 24

Fiber grade poly(ethylene terephthalate) (PET) is dry blended with testadditives, then melt compounded at 550° F. and then pelletized. Thepolyester pellets are dried at 175° F. for 24 hours under vacuum. Thedried pellets are extruded into fibers using a Hills laboratory scalefiber extruder at 550° F. Socks are knitted from these fibers and testedfor flame retardancy according to NFPA 701 test method.

The fibers containing a compound selected from NOR1–NOR12, a classicflame retardant and a present acid scavenger exhibit excellent flameretardancy.

EXAMPLE 25

Thermoplastic resins including polypropylene, polyethylene homopolymer,polyolefin copolymer or thermoplastic olefins (TPO), high impactpolystyrene (HIPS) and ABS are dry blended with test additives and thenmelt compounded into pellets. The pelletized fully formulated resin isthen processed into a useful article such as extrusion into fiber; blownor cast extrusion into film; blow molded into bottles; injection moldedinto molded articles, thermoformed into molded articles, extruded intowire and cable housing or rotation molded into hollow articles.

The articles containing a compound selected from NOR1–NOR12, a knownconventional flame retardant and a present acid scavenger exhibitexcellent flame retardancy when tested by a known standard test method.

Polyethylene wire and cable applications are tested for flame retardancyaccording to ASTM D-2633–82 burn test method. The materials containing acompound selected from NOR1–NOR12, a conventional flame retardant and apresent acid scavenger show excellent flame retardancy.

EXAMPLE 26

Articles prepared according to Example 25 which additionally contain anorganophosphorus stabilizer selected from the group consisting oftris(2,4-di-tert-butylphenyl)phosphite,bis(2,4-di-tert-butyl-6-methylphenyl)ethyl phosphite,2,2′,2″-nitrilo[triethyl-tris(3,3′,5,5′-tetra-tert-butyl-1,1′-biphenyl-2,2′-diyl)phosphite],tetrakis(2,4-di-butylphenyl) 4,4′-biphenylenediphosphonite,tris(nonylphenyl)phosphite, bis(2,4-di-tert-butylphenyl)pentaerythrityldiphosphite, 2,2′-ethylidenebis(2,4-di-tert-butylphenyl)fluorophosphiteand 2-butyl-2-ethylpropan-1,3-diyl 2,4,6-tri-tert-butylphenyl phosphiteexhibit good flame retardancy properties.

EXAMPLE 27

Articles prepared according to Example 25 which additionally contain ao-hydroxyphenyl-2H-benzotriazole, a hydroxyphenyl benzophenone or ao-hydroxyphenyl-s-triazine UV absorber selected from the groupconsisting of 2-(2-hydroxy-3,5-di-α-cumylphenyl)-2H-benzotriazole,2-(2-hydroxy-5-methylphenyl)-2H-benzotriazole,5-chloro-2-(2-hydroxy-3,5-di-tert-butylphenyl)-2H-benzotriazole,2-(2-hydroxy-3,5-di-tert-amylphenyl)-2H-benzotriazole,2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole,2,4-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate,2-hydroxy-4-n-octyloxybenzophenone and2,4-bis(2,4-dimethyphenyl)-6-(2-hydroxy-4-octyloxyphenyl)-s-triazineexhibit good flame retardancy.

1. A flame retardant polymer composition which comprises (a) an organicpolymer substrate and (b) an effective flame retarding amount of asynergistic mixture of (i) at least one sterically hindered aminestabilizer, (ii) tris[3-bromo-2,2-bis(bromomethyl)propyl] phosphate andwhere the stabilizers of component (i) are of the formula

where G₁ and G₂ are independently alkyl of 1 to 8 carbon atoms or aretogether pentamethylene, Z₁ and Z₂ are each methyl, or Z₁ and Z₂together form a linking moiety which may additionally be substituted byan ester, ether, amide, amino, carboxy or urethane group, and E iscyclohexyloxy; and where the hydrotalcite are present from about 0.1% toabout 1.0% by weight based on component (a).
 2. A composition accordingto claim 1 containing no flame retardant or conventional filler or aflame retardant or conventional filler in an amount less than 3% byweight based on the weight of the polymer component (a).
 3. Acomposition according to claim 1 containing no antimony compounds orantimony compounds in an amount less than 1% by weight based on theweight of component (a).
 4. A composition according to claim 1 in whichthe polymer component (a) is a thermoplastic polymer.
 5. A compositionaccording to claim 1 in which the polymer component (a) is selected fromthe group of resins consisting of the polyolefins, the thermoplasticolefins, styrenic polymers and copolymers, ABS and polymers whichcontain hetero atoms, double bonds or aromatic rings.
 6. A compositionaccording to claim 1 in which the polymer component (a) is selected frompolyethylene, polypropylene or copolymers thereof.
 7. A compositionaccording to claim 1 in which component (i) is a mixture ofN,N′,N′″-tris{2,4-bis[(1-hydrocarbyloxy-2,2,6,6-tetramethylpiperidin-4-yl)alkylamino]-s-triazin-6-yl}-3,3′-ethylenediiminodipropylamine;N,N′,N″-tris{2,4-bis[(1-hydrocarbyloxy-2,2,6,6-tetramethylpiperidin-4-yl)alkylamino]-s-triazin-6-yl}-3,3′-ethylenediiminodipropylamine,and bridged derivatives as described by formulas I, II, IIA and IIIR₁NH—CH₂CH₂CH₂NR₂CH₂CH₂NR₃CH₂CH₂CH₂NHR₄  (I)T-E₁-T₁  (II)T-E₁  (IIA)G-E₁-G₁-E₁-G₂  (III) where in the tetraamine of formula I R₁ and R₂ arethe s-triazine moiety E; and one of R₃ and R₄ is the s-triazine moiety Ewith the other of R₃ or R₄ being hydrogen, E is

R is, R₅ is alkyl of 1 to 12 carbon atoms, where in the compound offormula II or IIA, T and T₁ are each a tetraamine substituted by R₁–R₄as is defined for formula I, where (1) one of the s-triazine moieties Ein each tetraamine is replaced by the group E₁ which forms a bridgebetween two tetraamines T and T₁, E₁ is

or (2) the group E₁ can have both termini in the same tetraamine T as informula IIA where two of the E moieties of the tetraamine are replacedby one E₁ group, or (3) all three s-triazine substituents of tetraamineT can be E₁ such that one E₁ links T and T₁ and a second E₁ has bothtermini in tetraamine T, L is; where in the compound of formula III G,G₁ and G₂ are each tetraamines substituted by R₁–R₄ as defined forformula I, except that G and G₂ each have one of the s-triazine moietiesE replaced by E₁, and G₁ has two of the triazine moieties E replaced byE₁, so that there is a bridge between G and G₁ and a second bridgebetween G₁ and G₂; which mixture is prepared by reacting two to fourequivalents of2,4-bis[(1-hydrocarbyloxy-2,2,6,6-tetramethylpiperidin-4-yl)butylamino]-6-chloro-s-triazinewith one equivalent of N,N′-bis(3-aminopropyl)ethylenediamine.
 8. Acomposition according to claim 1 wherein the stabilizers of component(i) are selected from the group consisting of1-cyclohexyloxy-2,2,6,6-tetramethyl-4-octadecylaminopiperidine;2,4-bis[(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)butylamino]-6-(2-hydroxyethylamino-s-triazine;bis(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)adipate;2,4-bis[(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)butylamino]-6-chloro-s-triazine;and the reaction product of2,4-bis[(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)-butylamino]-6-chloro-s-triazinewith N,N′-bis(3-aminopropyl)ethylenediamine).
 9. A composition accordingto claim 1 in which the stabilizers of component (i) are present fromabout 0.05% to about 20% by weight based on the polymer substrate (a).10. A composition according to claim 1 in which the stabilizers ofcomponent (i) are present from about 0.1% to about 10% by weight basedon the polymer substrate (a).
 11. A composition according to claim 1 inwhich component (ii) is present in an amount from about 0.5% to about45% by weight based on the polymeric substrate (a).
 12. A compositionaccording to claim 1 in which the acid scavengers of component (ii) arepresent from about 0.2% to about 0.8% by weight based on component (a).13. A composition according to claim 1 comprising a further componentselected from the group consisting of pigments, dyes, plasticizers,phenolic antioxidants, thixotropic agents, levelling assistants, basiccostabilizers, nitrone stabilizers, amine oxide stabilizers,benzofuranone stabilizers, UV absorbers, sterically hindered amines,metal passivators, metal oxides, organophosphorus compounds,hydroxylamines, and mixtures thereof.
 14. A composition according toclaim 13 in which the further component is selected from the groupconsisting of phenolic antioxidants, calcium stearate, zinc stearate, orphosphite phosphonite stabilizers, benzofuranone stabilizers, UVabsorbers of the 2-(2′-hydroxyphenyl)benzotriazole or2-(2-hydroxyphenyl)-1,3,5-triazine classes, and sterically hinderedamines.
 15. A process for imparting light stability and flame retardancyto an organic polymer substrate, which process comprises adding to saidpolymer substrate (i) at least one sterically hindered amine stabilizer,(ii) tris[3-bromo-2,2-bis(bromomethyl)propyl]phosphate and where thestabilizers of component (i) are of the formula

where G₁ and G₂ are independently alkyl of 1 to 8 carbon atoms or aretogether pentamethylene, Z₁ and Z₂ are each methyl, or Z₁ and Z₂together form a linking moiety which may additionally be substituted byan ester, ether, amide, amino, carboxy or urethane group, and E iscyclohexyloxy; and where the hydrotalcite are present from about 0.1% toabout 1.0% by weight based on the polymer substrate.
 16. A compositionaccording to claim 1 which is a construction article selected from thegroup consisting of roofing membranes, window profiles, siding andmoldings.
 17. A composition according to claim 1 which is athermoplastic polyolefin article.